FIELD OF THE INVENTION
[0001] The present invention relates to a polyamide resin composition, and more particularly
to a polyamide resin composition having excellent moldability and capable of providing
molded products of excellent flexibility, low-temperature impact resistance, resistance
to water absorption and resistance to saline solutions.
BACKGROUND OF THE INVENTION
[0002] Because of excellent properties of polyamide resins, they are expected to be in great
demand as engineering plastics. However, some properties of the polyamide resins,
such as flexibility, low-temperature impact resistance, resistance to water absorption
and resistance to saline solutions, are not always sufficient, and therefore various
improvements of these properties have been studied. If the polyamide resins are improved
in the flexibility and low-temperature impact resistance, they can be applied to wide
uses of from sports goods such as ski boots and sports shoes to industrial parts such
as automobile parts, oil tubes, flexible tubes and air hoses, and a great demand therefor
can be expected.
[0003] For improving the flexibility and the water resistance such as resistance to water
absorption or resistance to saline solutions of the polyamide resins, a method of
adding ethylene/α,β-unsaturated monocarboxylic acid copolymer neutralized products
(ionomer resins) to the polyamide resins is proposed in Japanese Patent Laid-Open
Publications No. 80014/1978, No. 167751/1981, No. 109247/1981 and No. 157451/1981.
[0004] However, the polyamide resin compositions proposed in these publications exhibit
poor improved effects in the impact resistance such as Izod impact strength, particularly
impact resistance at low temperatures, though they can be improved in the water resistance
such as resistance to water absorption and resistance to saline solutions.
[0005] For improving the impact resistance such as Izod impact strength of the polyamide
resins, a method of adding ethylene/α-olefin copolymer grafted with α,β-unsaturated
carboxylic acids to the polyamide resins is proposed in, for example, Japanese Patent
Publications No. 12546/1967 and No. 44108/1980 and Japanese Patent Laid-Open Publication
No. 9662/1980.
[0006] However, the polyamide resin compositions proposed in these publications show insufficient
flexibility and impact resistance at low temperatures. In addition, these polyamide
resin compositions have poor moldability depending on the molding process.
[0007] As other method to improve the flexibility of the polyamide resins, a method of adding
an ethylene/propylene copolymer grafted with α,β-unsaturated carboxylic acid or an
ethylene-1-butene copolymer grafted with said acid to the polyamide resin in the amount
exceeding 2/3 of the amount of the polyamide resin and not more than 6 times by weight
as much as the polyamide resins is proposed in, for example, Japanese Patent Publication
No. 13379/1987.
[0008] However, the polyamide resin composition proposed in this publication still shows
insufficient impact resistance at low temperatures and poor moldability, though the
flexibility is satisfactory.
[0009] Accordingly, development of a polyamide resin composition having excellent moldability
and capable of providing molded products of excellent flexibility, low-temperature
impact resistance, resistance to water absorption and resistance to saline solutions
has been desired up to now.
OBJECT OF THE INVENTION
[0010] The present invention is intended to solve such problems associated with the prior
art as described above, and it is an object of the invention to provide a polyamide
resin composition having excellent moldability and capable of providing molded products
of excellent flexibility, low-temperature impact resistance, resistance to water absorption
and resistance to saline solutions.
SUMMARY OF THE INVENTION
[0011] A polyamide resin composition according to the invention is a polyamide resin composition
comprising:
[I] 100 parts by weight of a polyamide resin (A), and
[II] 5 to 200 parts by weight of a graft-modified ethylene/α-olefin random copolymer
(B) being obtained by graft-modifying an ethylene/α-olefin random copolymer of ethylene
and an α-olefin of 6 to 20 carbon atoms with an unsaturated carboxylic acid or its
derivative and having a graft quantity of 0.01 to 10 % by weight,
wherein the graft-modified ethylene/α-olefin random copolymer (B) is a graft-modified
product of an ethylene/α-olefin random copolymer having the following properties:
(a) the content of the α-olefin of 6 to 20 carbon atoms is in the range of 6 to 25
% by mol; and
(b) the intrinsic viscosity (η), as measured in decalin at 135 °C, is in the range
of 0.5 to 5.0 dl/g.
[0012] The ethylene/α-olefin random copolymer before the graft modification is preferably
an ethylene/α-olefin random copolymer obtained by copolymerizing ethylene and an α-olefin
of 6 to 20 carbon atoms in the presence of a metallocene catalyst.
[0013] The ethylene/α-olefin random copolymer before the graft modification is preferably
a linear or long-chain branched ethylene/α-olefin random copolymer having the properties
described below.
[0014] The linear ethylene/α-olefin random copolymer has the following properties:
(a) the content of the α-olefin of 6 to 20 carbon atoms is in the range of 6 to 25
% by mol;
(b) the intrinsic viscosity (η), as measured in decalin at 135 °C, is in the range
of 0.5 to 5.0 dl/g;
(c) the glass transition temperature (Tg) is not higher than -50 °C;
(d) the crystallinity, as measured by X-ray diffractometry, is less than 30 %;
(e) the molecular weight distribution (Mw/Mn), as determined by GPC, is not more than
3.0;
(f) the B value, as determined by the 13C-NMR spectrum and the following equation, is in the range of 1.0 to 1.4,

wherein PE and PO are a molar fraction of the ethylene component and a molar fraction of the α-olefin
component, respectively, contained in the unmodified ethylene/α-olefin random copolymer,
and POE is a proportion of the number of the ethylene/α-olefin alternating sequences to the
number of all the dyad sequences; and
(g) the ratio gη* of the intrinsic viscosity (η) determined in the property (b) to
the intrinsic viscosity (η)blank of a linear ethylene/propylene copolymer having the same weight-average molecular
weight (measured by a light scattering method) as said ethylene/α-olefin random copolymer
and having an ethylene content of 70 % by mol, (η)/(η)blank, is more than 0.95.
[0015] The long-chain branched ethylene/α-olefin random copolymer has the following properties:
(a) the content of the α-olefin of 6 to 20 carbon atoms is in the range of 6 to 25
% by mol;
(b) the intrinsic viscosity (η), as measured in decalin at 135 °C, is in the range
of 0.5 to 5.0 dl/g;
(c) the glass transition temperature (Tg) is not higher than -50 °C;
(d) the crystallinity, as measured by X-ray diffractometry, is less than 30 %;
(e) the molecular weight distribution (Mw/Mn), as determined by GPC, is not more than
3.0;
(f) the B value, as determined by the 13C-NMR spectrum and the above-mentioned equation, is in the range of 1.0 to 1.4; and
(g) the ratio gη* of the intrinsic viscosity (η) determined in the property (b) to
the intrinsic viscosity (η)blank of a linear ethylene/propylene copolymer having the same weight-average molecular
weight (measured by a light scattering method) as said ethylene/α-olefin random copolymer
and having an ethylene content of 70 % by mol, (η)/(η)blank, is in the range of 0.2 to 0.95.
[0016] The linear ethylene/α-olefin random copolymer having the above properties is preferably
a copolymer obtained by random copolymerizing ethylene and an α-olefin of 6 to 20
carbon atoms in the presence of a metallocene catalyst containing a metallocene compound
represented by the following formula [C-a] or [B-a]:

wherein M is a transition metal of Group IVB of the periodic table,
R11 and R12 are each hydrogen, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms which
may be substituted for halogen, a silicon-containing group, an oxygen-containing group,
a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing
group,
R13 and R14 are each an alkyl group of 1 to 20 carbon atoms,
X1 and X2 are each hydrogen, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms, a
halogenated hydrocarbon group of 1 to 20 carbon atoms, an oxygen-containing group
or a sulfur-containing group, and
Y is a divalent hydrocarbon group of 1 to 20 carbon atoms, a divalent halogenated
hydrocarbon group of 1 to 20 carbon atoms, a divalent silicon-containing group, a
divalent germanium-containing group, -O-, -CO-, -S-, -SO-, -SO2-, -NR7-, -P(R7)-, -P(O)(R7)-, -BR7- or -AlR7- (R7 is hydrogen, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms or a halogenated
hydrocarbon group of 1 to 20 carbon atoms);

wherein M is a transition metal of Group IVB of the periodic table,
R21s may be the same as or different from each other and are each hydrogen, a halogen
atom, an alkyl group of 1 to 10 carbon atoms which may be halogenated, an aryl group
of 6 to 10 carbon atoms, -NR2, -SR, -OSiR3, -SiR3 or -PR2 (R is a halogen atom, an alkyl group of 1 to 10 carbon atoms or an aryl group of
6 to 10 carbon atoms),
R22 to R28 are each the same as R21, or adjacent two of R22 to R28 may form an aromatic or aliphatic ring together with atoms to which they are bonded,
X3 and X4 may be the same as or different from each other and are each hydrogen, a halogen
atom, an OH group, an alkyl group of 1 to 10 carbon atoms, an alkoxy group of 1 to
10 carbon atoms, an aryl group of 6 to 10 carbon atoms, an aryloxy group of 6 to 10
carbon atoms, an alkenyl group of 2 to 10 carbon atoms, an arylalkyl group of 7 to
40 carbon atoms, an alkylaryl group of 7 to 40 carbon atoms or an arylalkenyl group
of 8 to 40 carbon atoms, and
Z is

=BR
29, =AlR
29, -Ge-, -Sn-, -O-, -S-, =SO, =SO
2, =NR
29, =CO, =PR
29 or =P(O)R
29 (R
29 and R
30 may be the same as or different from each other and are each hydrogen, a halogen
atom, an alkyl group of 1 to 10 carbon atom, a fluoroalkyl group of 1 to 10 carbon
atoms, an aryl group of 6 to 10 carbon atoms, a fluoroaryl group of 6 to 10 carbon
atoms, an alkoxy group of 1 to 10 carbon atoms, an alkenyl group of 2 to 10 carbon
atoms, an arylalkyl group of 7 to 40 carbon atoms, an arylalkenyl group of 8 to 40
carbon atoms or an alkylaryl group of 7 to 40 carbon atoms, or R
29 and R
30 may form a ring together with atoms to which they are bonded, and M
2 is silicon, germanium or tin).
[0017] The long-chain branched ethylene/α-olefin random copolymer having the above properties
is preferably a copolymer obtained by random copolymerizing ethylene and an α-olefin
of 6 to 20 carbon atoms in the presence of a metallocene catalyst containing a metallocene
compound represented by the following formula [II] :

wherein M is a transition metal of Group IVB of the periodic table,
R1 is a hydrocarbon group of 1 to 6 carbon atoms,
R2, R4, R5 and R6 may be the same as or different from each other and are each hydrogen, a halogen
atom or a hydrocarbon group of 1 to 6 carbon atoms,
R3 is an aryl group of 6 to 16 carbon atoms, which may be substituted for a halogen
atom, a hydrocarbon group of 1 to 20 carbon atoms or an organosilyl group,
X1 and X2 are each hydrogen, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms, a
halogenated hydrocarbon group of 1 to 20 carbon atoms, an oxygen-containing group
or a sulfur-containing group, and
Y is a divalent hydrocarbon group of 1 to 20 carbon atoms, a divalent halogenated
hydrocarbon group of 1 to 20 carbon atoms, a divalent silicon-containing group, a
divalent germanium-containing group, -O-, -CO-, -S-, -SO-, -SO2-, -NR7-, -P(R7)-, -P(O)(R7)-, -BR7- or -AlR7- (R7 is hydrogen, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms or a halogenated
hydrocarbon group of 1 to 20 carbon atoms).
DETAILED DESCRIPTION OF THE INVENTION
[0018] A polyamide resin composition according to the invention is described in detail hereinafter.
[0019] The polyamide resin composition of the invention comprises a polyamide resin (A)
and a specific graft-modified ethylene/α-olefin random copolymer (B) in a specific
ratio.
Polyamide resin (A)
[0020] There is no specific limitation on the polyamide resin (A) used in the invention,
and the term "polyamide resin" used herein means all the polymers which are composed
of amino acid lactams or composed of diamines and carboxylic acids and have melt polymerizability
and melt moldability.
[0021] Examples of the polyamide resin (A) used in the invention include the following resins:
(1) polycondensates of organic dicarboxylic acids having 4 to 12 carbon atoms and
organic diamines having 2 to 13 carbon atoms, e.g., polyhexamethylene adipamide (nylon
6,6) which is a polycondensate of hexamethylenediamine and adipic acid, polyhexamethylene
azelamide (nylon 6,9) which is a polycondensate of hexamethylenediamine and azelaic
acid, polyhexamethylene sebacamide (nylon 6,10) which is a polycondensate of hexamethylenediamine
and sebacic acid, polyhexamethylene dodecanoamide (nylon 6,12) which is a polycondensate
of hexamethylenediamine and dodecanedioic acid, and polybis(4-aminocyclohexyl)methanedodecane
which is a polycondensate of bis-p-aminocyclohexylmethane and dodecanedioic acid;
(2) polycondensates of ω-amino acids, e.g., polyundecaneamide (nylon 11) which is
a polycondensate of ω-aminoundecanoic acid; and
(3) ring-opened polymers of lactams, e.g., polycaplamide (nylon 6) which is a ring-opened
polymer of ε-aminocaprolactam, and polylauric lactam (nylon 12) which is a ring-opened
polymer of ε-aminolaurolactam.
[0022] Of these, polyhexamethylene adipamide (nylon 6, 6), polyhexamethylene azelamide (nylon
6,9) and polycaplamide (nylon 6) are preferably employed.
[0023] In the present invention, a polyamide resin prepared from adipic acid, isophthalic
acid and hexamethylenediamine and a blend of two or more kinds of polyamide resins,
e.g., a blend of nylon 6 and nylon 6,6, are also employable.
[0024] The polyamide resins (1) can be prepared by, for example, polycondensation of organic
dicarboxylic acids having 4 to 12 carbon atoms and organic diamines having 2 to 13
carbon atoms in equimolar amounts. If desired, the organic dicarboxylic acid can be
used in a larger amount than the organic diamine so that the amount of the carboxyl
group becomes larger than that of the amino group in the resulting polyamide resin.
To the contrary, the organic dicarboxylic acid can be used in a smaller amount than
the organic diamine so that the amount of the amino group becomes larger than that
of the carboxyl group in the resulting polyamide resin.
[0025] Examples of the organic dicarboxylic acids include adipic acid, pimelic acid, suberic
acid, sebacic acid and dodecanedioic acid.
[0026] Examples of the organic diamines include hexamethylenediamine and octamethylenediamine.
[0027] The polyamide resins (1) can be also prepared from derivatives capable of producing
carboxylic acids, such as esters and acid chlorides, and derivatives capable of producing
amines, such as amine salts, in a manner similar to that described above.
[0028] The polyamide resins (2) can be prepared by, for example, polycondensation of ω-amino
acids under heating in the presence of a small amount of water. In many cases, a viscosity
stabilizer such as an acetic acid is added in a small amount.
[0029] The polyamide resins (3) can be prepared by, for example, ring-opening polymerizing
lactams under heating in the presence of a small amount of water. In many cases, a
viscosity stabilizer such as an acetic acid is added in a small amount.
Graft-modified ethylene/α-olefin random copolymer (B)
[0030] The graft-modified ethylene/α-olefin random copolymer (B) used in the invention is
obtained by graft-modifying an ethylene/α-olefin random copolymer comprising ethylene
and an α-olefin of 6 to 20 carbon atoms (sometimes referred to as "unmodified ethylene/α-olefin
random copolymer" hereinafter) with a specific amount of an unsaturated carboxylic
acid or its derivative.
[0031] Examples of the α-olefins of 6 to 20 carbon atoms include 1-hexene, 1-heptene, 1-octene,
1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene,
1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene,
3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene,
4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene
and 12-ethyl-1-tetradecene. These α-olefins can be used in combination.
[0032] The unmodified ethylene/α-olefin random copolymer has an α-olefin content of 6 to
25 % by mol, preferably 8 to 22 % by mol, more preferably 10 to 20 % by mol. When
the unmodified ethylene/α-olefin random copolymer having an α-olefin content within
the above range is used, a graft-modified ethylene/α-olefin random copolymer (B) having
good flexibility and ease of handling can be obtained. Further, when this graft-modified
ethylene/α-olefin random copolymer (B) is used, a polyamide resin composition capable
of providing molded products of excellent low-temperature impact resistance and flexibility
can be obtained.
[0033] The unmodified ethylene/α-olefin random copolymer has an intrinsic viscosity (η),
as measured in decalin at 135 °C, of 0.5 to 5.0 dl/g, preferably 1.5 to 3.0 dl/g.
The graft-modified ethylene/α-olefin random copolymer (B) obtained from the unmodified
ethylene/α-olefin random copolymer having an intrinsic viscosity (η) within the above
range exhibits good blending properties with the polyamide resin (A). Further, when
this graft-modified ethylene/α-olefin random copolymer (B) is used, a polyamide resin
composition having good moldability can be obtained.
[0034] The unmodified ethylene/α-olefin random copolymer having the above properties can
be prepared by random copolymerizing ethylene and an α-olefin of 6 to 20 carbon atoms
in the presence of a vanadium catalyst comprising a soluble vanadium compound and
an alkylaluminum halide compound or a zirconium catalyst comprising a metallocene
compound of zirconium and an organoaluminum oxy-compound, as described later.
[0035] Of various unmodified ethylene/α-olefin random copolymers having the above properties,
preferably used are linear and long-chain branched ethylene/α-olefin random copolymers
having the following properties.
[0036] The α-olefin content and the intrinsic viscosity of the linear ethylene/α-olefin
random copolymer preferably used in the invention are described above.
[0037] The linear ethylene/α-olefin random copolymer further has a glass transition temperature
(Tg), as determined by DSC (differential scanning calorimeter), of not higher than
-50 °C. When the graft-modified ethylene/α-olefin random copolymer (B) obtained from
the unmodified linear ethylene/α-olefin random copolymer having a glass transition
temperature (Tg) within the above range is used, a polyamide resin composition capable
of providing molded products of excellent low-temperature impact resistance and low-temperature
flexibility can be obtained.
[0038] The unmodified linear ethylene/α-olefin random copolymer has a melting point of not
higher than 90 °C.
[0039] The unmodified linear ethylene/α-olefin random copolymer has a crystallinity, as
measured by X-ray diffractometry, of less than 30 %, preferably not more than 20 %.
When the graft-modified ethylene/α-olefin random copolymer (B) obtained from the unmodified
linear ethylene/α-olefin random copolymer having a crystallinity of less than 30 %
is used, a polyamide resin composition having good moldability can be obtained.
[0040] It is preferable that the unmodified linear ethylene/α-olefin random copolymer has
a molecular weight distribution (Mw/Mn), as determined by GPC, of not more than 3.0,
and has a parameter (B value), which indicates randomness of the monomer sequence
distribution in the copqlymer, of 1.0 to 1.4.
[0041] The B value of the unmodified linear ethylene/α-olefin copolymer is an index of the
composition distribution of constituent units derived from each monomer in the sequences
in the copolymer, and it can be calculated by the following equation:

wherein P
E and P
O are a molar fraction of the ethylene component and a molar fraction of the α-olefin
component, respectively, contained in the unmodified ethylene/α-olefin random copolymer,
and P
OE is a proportion of the number of the ethylene/α-olefin alternating sequences to the
number of all the dyad sequences.
[0042] The values for P
E, P
O and P
OE can be determined in the following manner.
[0043] In a test tube having a diameter of 10 mm, about 200 mg of the unmodified ethylene/α-olefin
copolymer is homogeneously dissolved in 1 ml of hexachlorobutadiene to give a sample,
and a
13C-NMR spectrum of the sample was obtained by measuring under the following measuring
conditions.
Measuring conditions
[0044]
Measuring temperature: 120 °C
Measuring frequency: 20.05 MHz
Spectrum width: 1,500 Hz
Filter width: 1,500 Hz
Pulse repetition time: 4.2 sec
Pulse width: 7 µsec
Integrating times: 2,000 to 5,000
[0045] The P
E, P
O and P
OE values can be determined from the
13C-NMR spectrum thus obtained in accordance with the reports by G.J. Ray (Macromolecules,10,773
(1977)), J.C. Randall (Macromolecules,15,353 (1982)) and K. Kimura (Polymer,25,4418
(1984)).
[0046] The B value calculated by the above equation becomes 2 when the both monomers are
alternately distributed in the unmodified ethylene/α-olefin random copolymer, and
it becomes 0 when the both monomers are completely separated and polymerized to form
a complete block copolymer.
[0047] When the graft-modified ethylene/α-olefin random copolymer (B) obtained from the
unmodified ethylene/α-olefin random copolymer having a B value within the above range
is used, a polyamide resin composition capable of providing molded products of excellent
low-temperature impact resistance can be obtained.
[0048] The linear ethylene/α-olefin random copolymer has a gη* value, as determined by the
intrinsic viscosity (η) of said copolymer, of more than 0.95.
[0049] The gη* value is defined by the following equation:

wherein (η) is an intrinsic viscosity of the ethylene/α-olefin random copolymer measured
as above, and (η)
blank is an intrinsic viscosity of a linear ethylene/propylene copolymer which has the
same weight-average molecular weight (measured by a light scattering method) as the
ethylene/α-olefin random copolymer and has an ethylene content of 70 % by mol.
[0050] From the linear ethylene/α-olefin random copolymer having such properties as mentioned
above, a polyamide resin composition excellent in all of the mechanical properties,
weathering resistance, ozone resistance, low-temperature resistance (low-temperature
flexibility) and heat resistance and a molded product of the composition can be obtained.
[0051] The α-olefin content, intrinsic viscosity, glass transition temperature, crystallinity,
molecular weight distribution and B value of the long-chain branched ethylene/α-olefin
random copolymer preferably used in the invention are the same as those of the linear
ethylene/α-olefin random copolymer described above.
[0052] The gη* value of the long-chain branched ethylene/α-olefin random copolymer is in
the range of 0.2 to 0.95, preferably 0.4 to 0.9, more preferably 0.5 to 0.85. This
gη* value can be determined in the aforementioned manner.
[0053] By the fact the gη* value of the ethylene/α-olefin random copolymer is not more than
0.95 is indicated that a long-chain branch is formed in the molecule.
[0054] The linear and long-chain branched ethylene/α-olefin random copolymers preferably
used in the invention can be each prepared by random copolymerizing ethylene and an
α-olefin of 6 to 20 carbon atoms in the presence of a metallocene catalyst containing
the corresponding specific metallocene compound.
Preparation of unmodified ethylene/α-olefin random copolymer
[0055] The unmodified ethylene/α-olefin random copolymer used in the invention can be prepared
by random copolymerizing ethylene and an α-olefin of 6 to 20 carbon atoms in the presence
of a vanadium catalyst comprising a soluble vanadium compound and an alkylaluminum
halide compound or a zirconium catalyst comprising a metallocene compound of zirconium
and an organoaluminum oxy-compound, as described above.
[0056] Examples of the soluble vanadium compounds used for the vanadium catalysts include
vanadium tetrachloride, vanadium oxytrichloride, vanadium monoethoxydichloride, vanadium
triacetylacetonate and oxyvanadium triacetylacetonate.
[0057] Examples of the alkylaluminum halide compounds used for the vanadium catalysts include
ethylaluminum dichloride, diethylaluminum monochloride, ethylaluminum sesquichloride,
diethylaluminum monobromide, diisobutylaluminum monochloride, isobutylaluminum dichloride
and isobutylaluminum sesquichloride.
[0058] Examples of the metallocene compounds of zirconium used for the zirconium catalysts
include ethylenebis(indenyl)zirconium dibromide, dimethylsilylenebis(2-methylindenyl)zirconium
dichloride, bis(cyclopentadienyl)zirconium dibromide and bis(dimethylcyclopentadienyl)zirconium
dichloride.
[0059] Examples of the organoaluminum oxy-compounds used for the zirconium catalysts include
aluminooxane and benzene-insoluble organoaluminum oxy-compounds.
[0060] The zirconium catalyst may contain an organoaluminum compound together with the metallocene
compound of zirconium and the organoaluminum oxy-compound.
[0061] Examples of the organoaluminum compounds include triisobutylaluminum, dimethylaluminum
chloride and methylaluminum sesquichloride.
[0062] Copolymerization of ethylene and the α-olefin using the vanadium catalyst or the
zirconium catalyst can be carried out in either a solution state, a suspension state
or an intermediate state between those states, and in each case an inert solvent is
preferably used as a reaction medium.
[0063] As described above, the linear and long-chain branched ethylene/α-olefin random copolymers
preferably used in the invention can be each prepared by random copolymerizing ethylene
and an α-olefin of 6 to 20 carbon atoms in the presence of a metallocene catalyst
containing the corresponding specific metallocene compound.
[0064] There is no specific limitation on the metallocene catalyst used herein, except that
the metallocene catalyst contains a metallocene compound [a]. For example, the metallocene
catalyst may be formed from the metallocene compound [a], and an organoaluminum oxy-compound
[b] and/or a compound [c] which reacts with the metallocene compound [a] to form an
ion pair, or it may be formed from the metallocene compound [a], the organoaluminum
oxy-compound [b] and/or the ion pair-forming compound [c], and an organoaluminum compound
[d].
Metallocene compound [a]
[0065] The metallocene compound [a] used in the preparation of the linear ethylene/α-olefin
copolymer rubber is, for example, a compound represented by the following formula
[I].
ML
x [I]
[0066] In the formula [I], M is a transition metal selected from Group IVB of the periodic
table, specifically, zirconium, titanium or hafnium, and x is a valence of the transition
metal.
[0067] L is a ligand coordinated to the transition metal. At least one ligand L is a ligand
having cyclopentadienyl skeleton, and the ligand having cyclopentadienyl skeleton
may have a substituent.
[0068] Examples of the ligands having cyclopentadienyl skeleton include cyclopentadienyl
group; alkyl or cycloalkyl substituted cyclopentadienyl groups, such as methylcyclopentadienyl,
ethylcyclopentadienyl, n- or i-propylcyclopentadienyl, n-, i-, sec- or t-butylcyclopentadienyl,
hexylcyclopentadienyl, octylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl,
tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, methylethylcyclopentadienyl,
methylpropylcyclopentadienyl, methylbutylcyclopentadienyl, methylhexylcyclopentadienyl,
methylbenzylcyclopentadienyl, ethylbutylcyclopentadienyl, ethylhexylcyclopentadienyl
and methylcyclohexylcyclopentadienyl; indenyl group; 4,5,6,7-tetrahydroindenyl group;
and fluorenyl group.
[0069] These groups may be substituted with halogen atoms or trialkylsilyl groups.
[0070] Of the above groups, particularly preferable are alkyl substituted cyclopentadienyl
groups.
[0071] When the compound represented by the formula [I] has two or more groups having cyclopentadienyl
skeleton as the ligands L, two of them may be bonded to each other through an alkylene
group such as ethylene or propylene, a substituted alkylene group such as isopropylidene
or diphenylmethylene, a silylene group, or a substituted silylene group such as dimethylsilylene,
diphenylsilylene or methylphenylsilylene.
[0072] Examples of L other than the ligand having cyclopentadienyl skeleton (sometimes referred
to simply as "other L" hereinafter) include hydrocarbon groups of 1 to 12 carbon atoms,
alkoxy groups, aryloxy groups, halogen atoms, hydrogen and sulfonic acid-containing
groups (-SO
3R
a wherein the R
a is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group,
or an aryl group substituted with a halogen atom or an alkyl group).
[0073] Examples of the hydrocarbon groups of 1 to 12 carbon atoms include alkyl groups,
cycloalkyl groups, aryl groups and aralkyl groups.
[0074] More specifically, there can be mentioned:
alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,
t-butyl, pentyl, hexyl, octyl, decyl and dodecyl;
cycloalkyl groups, such as cyclopentyl and cyclohexyl;
aryl groups, such as phenyl and tolyl; and
aralkyl group, such as benzyl and neophyl.
[0075] Examples of the alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,
isobutoxy, sec-butoxy, t-butoxy, pentoxy, hexoxy and octoxy.
[0076] Examples of the aryloxy groups include phenoxy.
[0077] Examples of the sulfonic acid-containing group (-SO
3R
a) include methanesulfonato, p-toluenesulfonato, trifluoromethansulfonate and p-chlorobenzenesulfonato.
[0078] Examples of the halogen atoms include fluorine, chlorine, bromine and iodine.
[0079] The metallocene compound of the above formula wherein the valence of the transition
metal is 4 is more is specifically represented by the following formula [I-a]:
R
2 KR
3 lR
4 mR
5 nM [I-a]
wherein M is the above-mentioned transition metal, R
2 is a group (ligand) having cyclopentadienyl skeleton, R
3, R
4 and R
5 are each independently a group having cyclopentadienyl skeleton or the other L in
the above formula [I], k is an integer of not less than 1, and k+l+m+n = 4.
[0080] Listed below are examples of the metallocene compounds containing zirconium as M
and containing at least two ligands having cyclopentadienyl skeleton.
[0081] Bis(cyclopentadienyl)zirconium monochloride monohydride,
Bis(cyclopentadienyl)zirconium dichloride,
Bis(cyclopentadienyl)zirconium dibromide,
Bis(cyclopentadienyl)methylzirconium monochloride,
Bis(cyclopentadienyl)zirconium phenoxymonochloride,
Bis(methylcyclopentadienyl)zirconium dichloride,
Bis(ethylcyclopentadienyl)zirconium dichloride,
Bis(n-propylcyclopentadienyl)zirconium dichloride,
Bis(isopropylcyclopentadienyl)zirconium dichloride,
Bis(t-butylcyclopentadienyl)zirconium dichloride,
Bis(n-butylcyclopentadienyl)zirconium dichloride,
Bis(sec-butylcyclopentadienyl)zirconium dichloride,
Bis(isobutylcyclopentadienyl)zirconium dichloride,
Bis(hexylcyclopentadienyl)zirconium dichloride,
Bis(octylcyclopentadienyl)zirconium dichloride,
Bis(indenyl)zirconium dichloride,
Bis(4,5,6,7-tetrahydroindenyl)zirconium dichloride,
Bis(indenyl)zirconium dibromide,
Bis(cyclopentadienyl)zirconium dimethyl,
Bis(cyclopentadienyl)zirconium methoxychloride,
Bis(cyclopentadienyl)zirconium ethoxychloride,
Bis(fluorenyl)zirconium dichloride,
Bis(cyclopentadienyl)zirconiumbis(methanesulfonato),
Bis(cyclopentadienyl)zirconiumbis(p-toluenesulfonato),
Bis(cyclopentadienyl)zirconiumbis(trifluoromethanesulfonato),
Bis(methylcyclopentadienyl)zirconiumbis(trifluoromethanesulfonato),
Bis(ethylcyclopentadienyl)zirconiumbis(trifluoromethanesulfonato),
Bis(propylcyclopentadienyl)zirconiumbis(trifluoromethanesulfonato),
Bis(butylcyclopentadienyl)zirconiumbis(trifluoromethanesulfonato),
Bis(hexylcyclopentadienyl)zirconiumbis(trifluoromethanesulfonato),
Bis(1,3-dimethylcyclopentadienyl)zirconiumbis(trifluoromethanesulfonato),
Bis(1-methyl-3-ethylcyclopentadienyl)zirconiumbis(trifluoromethanesulfonato),
Bis(1-methyl-3-propylcyclopentadienyl)zirconiumbis(trifluoromethanesulfonato),
Bis(1-methyl-3-butylcyclopentadienyl)zirconiumbis(trifluoromethanesulfonato),
Bis(1,3-dimethylcyclopentadienyl)zirconium dichloride,
Bis(1-methyl-3-ethylcyclopentadienyl)zirconium dichloride,
Bis(1-methyl-3-propylcyclopentadienyl)zirconium dichloride,
Bis(1-methyl-3-butylcyclopentadienyl)zirconium dichloride,
Bis(1-methyl-3-hexylcyclopentadienyl)zirconium dichloride,
Bis(1-methyl-3-octylcyclopentadienyl)zirconium dichloride,
Bis(1-ethyl-3-butylcyclopentadienyl)zirconium dichloride,
Bis(trimethylcyclopentadienyl)zirconium dichloride,
Bis(tetramethylcyclopentadienyl)zirconium dichloride,
Bis(pentamethylcyclopentadienyl)zirconium dichloride,
Bis(methylbenzylcyclopentadienyl)zirconium dichloride,
Bis(eyhylhexylcyclopentadienyl)zirconium dichloride, and
Bis(methylcyclohexylcyclopentadienyl)zirconium dichloride.
[0082] Also employable in the invention are compounds wherein the 1,3-position substituted
cyclopentadienyl group is replaced with a 1,2-position substituted cyclopentadienyl
group in the above-exemplified compounds.
[0083] Further, also employable is a bridge type metallocene compound represented by the
above formula [I-a] wherein at least two of R
2, R
3, R
4 and R
5, e.g., R
2 and R
3, are groups (ligands) having cyclopentadienyl skeleton, and these at least two groups
are bonded to each other through an alkylene group, a substituted alkylene group,
a silylene group or a substituted silylene group. In this case, R
4 and R
5 are each independently the other L, which is described in the formula [I].
[0084] Listed below are examples of such bridge type metallocene compounds.
Ethylenebis(indenyl)dimethylzirconium,
Ethylenebis(indenyl)zirconium dichloride,
Ethylenebis(indenyl)zirconiumbis(trifluoromethanesulfonato),
Ethylenebis(indenyl)zirconiumbis(methanesulfonato),
Ethylenebis(indenyl)zirconiumbis(p-toluenesulfonato),
Ethylenebis(indenyl)zirconiumbis(p-chlorobenzenesulfonato),
Ethylenebis(4,5,6,7-tetrahydroindenyl)zirconium dichloride,
Isopropylidene(cyclopentadienyl-fluorenyl)zirconium dichloride,
Isopropylidene(cyclopentadienylmethylcyclopentadienyl)zirconium dichloride,
Dimethylsilylenebis(cyclopentadienyl)zirconium dichloride,
Dimethylsilylenebis(methylcyclopentadienyl)zirconium dichloride,
Dimethylsilylenebis(dimethylcyclopentadienyl)zirconium dichloride,
Dimethylsilylenebis(trimethylcyclopentadienyl)zirconium dichloride,
Dimethylsilylenebis(indenyl)zirconium dichloride,
Dimethylsilylenebis(indenyl)zirconiumbis(trifluoromethanesulfonato),
Dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)zirconium dichloride,
Dimethylsilylenebis(cyclopentadienylfluorenyl)zirconium dichloride,
Diphenylsilylenebis(indenyl)zirconium dichloride, and
Methylphenylsilylenebis(indenyl)zirconium dichloride.
[0085] Furthermore, a metallocene compound of the following formula [A], which is described
in Japanese Patent Laid-Open Publication No. 268307/1992, is also employable.

[0086] In the formula (A), M
1 is a metal of Group IVB of the periodic table, specifically, titanium, zirconium
or hafnium.
[0087] R
1 and R
2 may be the same as or different from each other and are each hydrogen, an alkyl group
of 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms, an alkoxy group of 1 to 10
carbon atoms, preferably 1 to 3 carbon atoms, an aryl group of 6 to 10 carbon atoms,
preferably 6 to 8 carbon atoms, an aryloxy group of 6 to 10 carbon atoms, preferably
6 to 8 carbon atoms, an alkenyl group of 2 to 10 carbon atoms, preferably 2 to 4 carbon
atoms, an arylalkyl group of 7 to 40 carbon atoms, preferably 7 to 10 carbon atoms,
an alkylaryl group of 7 to 40 carbon atoms, preferably 7 to 12 carbon atoms, an arylalkenyl
group of 8 to 40 carbon atoms, preferably 8 to 12 carbon atoms, or a halogen atom,
preferably chlorine.
[0088] R
3 and R
4 may be the same as or different from each other, and are each hydrogen, a halogen
atom, preferably fluorine, chlorine or bromine, an alkyl group of 1 to 10 carbon atoms,
preferably 1 to 4 carbon atoms, which may be halogenated, an aryl group of 6 to 10
carbon atoms, preferably 6 to 8 carbon atoms, or a group of -NR
102, -SR
10, -OSiR
103, -SiR
103 or -PR
102 (the R
10 is a halogen atom, preferably chlorine, an alkyl group of 1 to 10 carbon atoms, preferably
1 to 3 carbon atoms, or an aryl group of 6 to 10 carbon atoms, preferably 6 to 8 carbon
atoms).
[0089] R
3 and R
4 are each preferably hydrogen.
[0090] R
5 and R
6 may be the same as or different from each other, preferably the same as each other,
and R
5 and R
6 are the same as R
3 and R
4, but each of R
5 and R
6 is not hydrogen. R
5 and R
6 are each preferably an alkyl group of 1 to 4 carbon atoms which may be halogenated,
specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl or trifluoromethyl,
preferably methyl.
[0091] R
7 is represented by the following formulae:

=BR
11, =AlR
11, -Ge-, -Sn-, -O-, -S-, =SO, =SO
2, =NR
11, =CO, =PR
11 or =P(O)R
11 wherein the R
11, R
12 and R
13 may be the same as or different from each other; and they are each hydrogen, a halogen
atom, an alkyl group of 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, more
preferably methyl, a fluoroalkyl group of 1 to 10 carbon atoms, preferably CF
3, an aryl group of 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, a fluoroaryl
group of 6 to 10 carbon atoms, preferably pentafluorophenyl, an alkoxy group of 1
to 10 carbon atoms, preferably 1 to 4 carbon atoms, particularly preferably methoxy,
an alkenyl group of 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms, an arylalkyl
group of 7 to 40 carbon atoms, preferably 7 to 10 carbon atoms, an arylalkenyl group
of 8 to 40 carbon atoms, preferably 8 to 12 carbon atoms, or an alkylaryl group of
7 to 40 carbon atoms, preferably 7 to 12 carbon atoms; or R
11 and R
12 or R
11 and R
13 may form a ring together with a carbon atom to which they are bonded.
[0092] M
2 is silicon, germanium or tin, preferably silicon or germanium.
[0093] R
7 is preferably =CR
11R
12, =SiR
11R
12, =GeR
11R
12, -O-, -S-, =SO, =PR
11 or =P(O)R
11.
[0094] R
8 and R
9 may be the same as or different from each other, and they are the same as R
11.
[0095] m and n may be the same as or different from each other, and are each 0, 1 or 2,
preferably 0 or 1, and m+n is 0, 1 or 2, preferably 0 or 1.
[0096] Particularly preferred metallocene compounds satisfying the above conditions are
those represented by the following formulae (i) to (iii).

[0097] In the above formulae (i), (ii) and (iii), M
1 is Zr or Hf, R
1 and R
2 are each methyl or chlorine, R
5 and R
6 are each methyl, ethyl or trifuoromethyl, and R
8, R
9, R
11 and R
12 are the same as ones described above.
[0098] Of the compounds represented by the formulae (i), (ii) and (iii), the following compounds
are particularly preferable.
rac-Ethy[ene(2-methyl-1-indenyl)2-zirconium dichloride,
rac-Dimethylsilylene(2-methyl-1-indenyl)2-zirconium dichloride,
rac-Dimethylsilylene(2-methyl-1-indenyl)2-zirconium dimethyl,
rac-Ethylene(2-methyl-1-indenyl)2-zirconium dimethyl,
rac-Phenyl(methyl)silylene-(2-methyl-1-indenyl)2-zirconium dichloride,
rac-Diphenyl-silylene-(2-methyl-1-indenyl)2-zirconium dichloride,
rac-Methylethylene(2-methyl-1-indenyl)2-zirconium dichloride, and
rac-Dimethylsilylene(2-ethyl-1-indenyl)2-zirconium dichloride.
[0099] The metallocene compounds mentioned above can be prepared by conventionally known
processes (see: Japanese Patent Laid-Open Publication No. 268307/1992).
[0100] In the present invention, a transition metal compound (metallocene compound) represented
by the following formula [B] is also employable.

[0101] In the formula [B], M is a transition metal atom of Group IVB of the periodic table,
specifically, titanium, zirconium or hafnium.
[0102] R
1 and R
2 are each independently hydrogen, a halogen atom, a hydrocarbon group of 1 to 20 carbon
atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, a silicon-containing
group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing
group or a phosphorus-containing group.
[0103] Examples of the halogen atoms include fluorine, chlorine, bromine and iodine.
[0104] Examples of the hydrocarbon groups of 1 to 20 carbon atoms include alkyl groups,
such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl,
norbornyl and adamantyl; alkenyl groups, such as vinyl, propenyl and cyclohexenyl;
arylalkyl groups, such as benzyl, phenylethyl and phenylpropyl; and aryl groups, such
as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl,
naphthyl, methylnaphthyl, anthracenyl and phenanthryl.
[0105] Examples of the halogenated hydrocarbon groups include those wherein the above-exemplified
hydrocarbon groups are substituted with halogen atoms.
[0106] Examples of the silicon-containing groups include monohydrocarbon-substituted silyl
groups, such as methylsilyl and phenylsilyl; dihydrocarbon-substituted silyl groups,
such as dimethylsilyl and diphenylsilyl; trihydrocarbon-substituted silyl groups,
such as trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl,
dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl and trinaphthylsilyl; silyl
ethers of the hydrocarbon-substituted silyls, such as trimethylsilyl ether; silicon-substituted
alkyl groups, such as trimethylsilylmethyl; and silicon-substituted aryl groups, such
as trimethylsilylphenyl.
[0107] Examples of the oxygen-containing groups include hydroxyl group; alkoxy groups, such
as methoxy, ethoxy, propoxy and butoxy; aryloxy groups, such as phenoxy, methylphenoxy,
dimethylphenoxy and naphthoxy; and arylalkoxy groups, such as phenylmethoxy and phenylethoxy.
[0108] Examples of the sulfur-containing groups include substituents wherein oxygen is replaced
with sulfur in the above-exemplified oxygen-containing groups.
[0109] Examples of the nitrogen-containing groups include amino group; alkylamino groups,
such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino and
dicyclohexylamino; and arylamino or alkylarylamino groups, such as phenylamino, diphenylamino,
ditolylamino, dinaphthylamino and methylphenylamino.
[0110] Examples of the phosphorus-containing groups include phosphino groups, such as dimethylphosphino
and diphenylphosphino.
[0111] Of these, R
1 is preferably a hydrocarbon group, particularly preferably a hydrocarbon group of
1 to 3 carbon atoms, i.e., methyl, ethyl or propyl. R
2 is preferably hydrogen or a hydrocarbon group, particularly preferably hydrogen or
a hydrocarbon group of 1 to 3 carbon atoms, i.e., methyl, ethyl or propyl.
[0112] R
3, R
4, R
5 and R
6 are each independently hydrogen, a halogen atom, a hydrocarbon group of 1 to 20 carbon
atoms or a halogenated hydrocarbon group of 1 to 20 carbon atoms. Of these, hydrogen,
the hydrocarbon group or the halogenated hydrocarbon group is preferable. At least
one pair out of pairs of R
3 and R
4, R
4 and R
5, and R
5 and R
6 may form a monocyclic aromatic ring together with a carbon atom to which they are
bonded.
[0113] When there are two or more hydrocarbon groups or halogenated hydrocarbon, groups,
the groups other than those for forming the aromatic ring may be bonded to each other
to form a ring. When R
6 is a substituent other than the aromatic group, it is preferably hydrogen.
[0114] Examples of the halogen atoms, the hydrocarbon groups of 1 to 20 carbon atoms and
the halogenated hydrocarbon groups of 1 to 20 carbon atoms are the same as those described
for R
1 and R
2.
[0115] Examples of the ligands, which contain a monocyclic aromatic ring formed by at least
one pair of R
3 and R
4, R
4 and R
5, and R
5 and R
6 and which is coordinated to M, include the following ones.

[0116] Of these, the ligand represented by the formula (1) is preferable.
[0117] The aromatic ring may be substituted with a halogen atom, a hydrocarbon group of
1 to 20 carbon atoms or a halogenated hydrocarbon group of 1 to 20 carbon atoms.
[0118] Examples of the halogen atoms, the hydrocarbon groups of 1 to 20 carbon atoms and
the halogenated hydrocarbon groups of 1 to 20 carbon atoms used as the substituents
of the aromatic ring are the same as those described for R
1 and R
2.
[0119] X
1 and X
2 are each independently hydrogen, a halogen atom, a hydrocarbon group of 1 to 20 carbon
atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, an oxygen-containing
group or a sulfur-containing group.
[0120] Examples of the halogen atoms, the hydrocarbon groups of 1 to 20 carbon atoms, the
halogenated hydrocarbon groups of 1 to 20 carbon atoms and the oxygen-containing groups
are the same as those described for R
1 and R
2.
[0121] Examples of the sulfur-containing groups include the same groups as described for
R
1 and R
2; sulfonato groups, such as methylsulfonato, trifluoromethanesulfonato, phenylsulfonato,
benzylsulfonato, p-toluenesulfonato, trimethylbenzenesulfonato, triisobutylbenzenesulfonato,
p-chlorobenzenesulfonato and pentafluorobenzenesulfonato; and sulfinato groups, such
as methylsulfinato, phenylsulfinato, benzylsulfinato, p-toluenesulfinato, trimethylbenzenesulfinato
and pentafluorobenzenesulfinato.
[0122] Y is a divalent hydrocarbon group of 1 to 20 carbon atoms, a divalent halogenated
hydrocarbon group of 1 to 20 carbon atoms, a divalent silicon-containing group, a
divalent germanium-containing group, a divalent tin-containing group, -O-, -CO-, -S-,
-SO-, -SO
2-, -NR
7-, -P(R
7)-, -P(O)(R
7) -, -BR
7- or -AlR
7- (the R
7 is hydrogen, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms or a halogenated
hydrocarbon group of 1 to 20 carbon atoms).
[0123] Examples of the divalent hydrocarbon groups of 1 to 20 carbon atoms include alkylene
groups, such as methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene,
1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene; and
arylalkylene groups, such as diphenylmethylene and diphenyl-1,2-ethylene.
[0124] Examples of the divalent halogenated hydrocarbon groups include those wherein the
above-exemplified divalent hydrocarbon groups of 1 to 20 carbon atoms are halogenated,
such as chloromethylene.
[0125] Examples of the divalent silicon-containing groups include alkylsilylene, alkylarylsilylene
and arylsilylene groups, such as methylsilylene, dimethylsilylene, diethylsilylene,
di(n-propyl)silylene, di(i-propyl)silylene, di(cyclohexyl)silylene, methylphenylsilylene,
diphenylsilylene, di(p-tolyl)silylene and di(p-chlorophenyl)silylene; and alkyldisilylene,
alkylaryldisilylene and aryldisilylene groups, such as tetramethyl-1,2-disilylene
and tetraphenyl-1,2-disilylene.
[0126] Examples of the divalent germanium-containing groups include those wherein silicon
is replaced with germanium in the above-exemplified divalent silicon-containing groups.
[0127] Examples of the divalent tin-containing groups include those wherein silicon is replaced
with tin in the above-exemplified divalent silicon-containing groups.
[0128] R
7 is the same halogen atom, hydrocarbon group of 1 to 20 carbon atoms or halogenated
hydrocarbon group of 1 to 20 carbon atoms as described for R
1 or R
2.
[0129] Of the above groups, preferable are divalent silicon-containing groups, divalent
germanium-containing groups and divalent tin-containing group, and more preferable
are divalent silicon-containing groups. Among them, particularly preferable are alkylsilylene
groups, alkylarylsilylene groups and arylsilylene groups.
[0131] Also employable in the invention are transition metal compounds wherein zirconium
is replaced with titanium or hafnium in the above-mentioned compounds.
[0132] A racemic modification of the transition metal compound is generally used as the
olefin polymerization catalyst component, but R type or S type is also employable.
[0133] The indene derivative ligands of the transition metal compounds can be synthesized
in accordance with ordinary organic synthesis through, for example, the reaction route
described below.

A, B and D represent halogen atoms.
[0134] The transition metal compounds employable in the invention can be synthesized from
these indene derivatives in accordance with conventionally known processes, for example,
a process described in Japanese Patent Laid-Open Publication No. 268307/1992.
[0135] In the present invention, a transition metal compound (metallocene compound) represented
by the following formula [C] is also employable.

[0136] In the formula [C] , M, R
1, R
2, R
3, R
4, R
5 and R
6 are the same as those in the aforesaid formula [B].
[0137] Among R
3, R
4, R
5 and R
6, two groups including R
3 are preferably alkyl groups, and it is more preferred that R
3 and R
5, or R
3 and R
6 are alkyl groups. These alkyl groups are preferably secondary or tertiary alkyl groups,
and they may be substituted with halogen atoms or silicon-containing groups. Examples
of the halogen atoms and the silicon-containing groups include the same substituents
as described for R
1 and R
2.
[0138] Of the groups indicated by R
3, R
4, R
5 and R
6, groups other than the alkyl groups are each preferably hydrogen.
[0139] Examples of the alkyl groups (the hydrocarbon groups of 1 to 20 carbon atoms) include
chain alkyl groups and cyclic alkyl groups, such as methyl, ethyl, n-propyl, i-propyl,
n-butyl, i-butyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl,
nonyl, dodecyl, eicosyl, norbornyl and adamantyl; and arylalkyl groups, such as benzyl,
phenylethyl, phenylpropyl and tolylmethyl. These groups may contain a double bond
or a triple bond.
[0140] Two groups selected from R
3, R
4, R
5 and R
6 may be bonded to each other to form a monocyclic or polycyclic ring other than the
aromatic ring.
[0141] Examples of the halogen atoms are the same as those described for R
1 and R
2.
[0142] X
1, X
2, Y and R
7 are the same as those in the aforesaid formula [B].
[0143] Listed below are examples of the metallocene compounds (transition metal compounds)
represented by the formula [C].
rac-Dimethylsilylene-bis(4,7-dimethyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,4,7-trimethyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,4,6-trimethyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,5,6-trimethyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,4,5,6-tetramethyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,4,5,6,7-pentamethyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-n-propyl-7-methyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(4-i-propyl-7-methyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-i-propyl-6-methyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-methyl-6-i-propyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-i-propyl-5-methyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilyl-bis(2-methyl-4,6-di(i-propyI)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4,6-di(i-propyl)-7-methyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-i-butyl-7-methyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-sec-butyl-7-methyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4,6-di(sec-butyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-tert-butyl-7-methyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-cyclohexyl-7-methyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-benzyl-7-methyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-phenylethyl-7-methyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-phenyldichloromethyl-7-methyl-1-indenyl)zirconium
dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-chloromethyl-7-methyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-trimethylsilylmethyl-7-methyl-1-indenyl)zirconium
dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-trimethylsiloxymethyl-7-methyl-1-indenyl)zirconium
dichloride,
rac-Diethylsilylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconium dichloride,
rac-Di(i-propyl)silylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconium dichloride,
rac-Di(n-butyl)silylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconium dichloride,
rac-Di(cyclohexyl)silylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconium dichloride,
rac-Methylphenylsilylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconium dichloride,
rac-Diphenylsilylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconium dichloride,
rac-Diphenylsilylene-bis(2-methyl-4,6-di(i-propyl)-1-indenyl)zirconium dichloride,
rac-Di(p-tolyl)silylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconium dichloride,
rac-Di(p-chlorophenyl)silylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconium
dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconium dibromide,
rac-Dimethylsilylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconium dimethyl,
rac-Dimethylsilylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconium methylchloride,
rac-Dimethylsilylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconium-bis(methanesulfonato),
rac-Dimethylsilylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconium-bis(p-phenylsulfinato),
rac-Dimethylsilylene-bis(2-methyl-3-methyl-4-i-propyl-6-methyl-1-indenyl)zirconium
dichloride,
rac-Dimethylsilylene-bis(2-ethyl-4-i-propyl-6-methyl-1-indenyl)zirconium dichloride,
and
rac-Dimethylsilylene-bis(2-phenyl-4-i-propyl-6-methyl-1-indenyl)zirconium dichloride.
[0144] Also employable in the invention are transition metal compounds wherein zirconium
is replaced with titanium or hafnium in the above-exemplified compounds.
[0145] A racemic modification of the transition metal compound is generally used, but R
type or S type is also employable.
[0146] The indene derivative ligands of the transition metal compounds can be synthesized
in accordance with ordinary organic synthesis through, for example, the reaction route
previously described.
[0147] The transition metal compounds (metallocene compounds) represented by the formula
[C] can be synthesized from these indene derivatives in accordance with conventionally
known processes, for example, a process described in Japanese Patent Laid-Open Publication
No. 268307/1992.
[0148] Of the metallocene compounds mentioned above, compounds represented by the following
formulas [C-a] and [B-a] are particularly preferably employed. The metallocene compounds
represented by the formula [C-a] are included in the compounds represented by the
formula [C], and the metallocene compounds represented by the formula [B-a] are included
in the compounds represented by the formula [B].

[0149] In the formula [C-a], M is a transition metal atom of Group IVB of the periodic table,
specifically titanium, zirconium or hafnium, preferably zirconium.
R11 and R12
[0150] R
11 and R
12 are each hydrogen, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms which
may be halogenated, a silicon-containing group, an oxygen-containing group, a sulfur-containing
group, a nitrogen-containing group or a phosphorus-containing group.
[0151] Examples of the hydrocarbon groups of 1 to 20 carbon atoms include:
alkyl groups, such as methyl, ethyl, propyl, n-butyl, isobutyl, sec-butyl, tert-butyl,
pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl and
adamantyl;
alkenyl groups, such as vinyl, propenyl and cyclohexenyl;
arylalkyl groups, such as benzyl, phenylethyl and phenylpropyl; and
aryl groups, such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl,
propylphenyl, biphenyl, α- or β-naphthyl, methylnaphthyl, anthracenyl, phenanthryl,
benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl,
indanyl and biphenylyl.
[0152] These hydrocarbon groups may be substituted with halogen atoms such as fluorine,
chlorine, bromine and iodine, or organosilyl groups such as trimethylsilyl, triethylsilyl
and triphenylsilyl.
[0153] Examples of the oxygen-containing groups include hydroxyl group; alkoxy groups, such
as methoxy, ethoxy, propoxy and butoxy; aryloxy groups, such as phenoxy, methylphenoxy,
dimethylphenoxy and naphthoxy; and arylalkoxy groups, such as phenylmethoxy and phenylethoxy.
[0154] Examples of the sulfur-containing groups include substituents wherein oxygen is replaced
with sulfur in the above-exemplified oxygen-containing groups; sulfonato groups, such
as methylsulfonato, trifluoromethanesulfonato, phenylsulfonato, benzylsulfonato, p-toluenesulfonato,
trimethylbenzenesulfonato, triisobutylbenzenesulfonato, p-chlorobenzenesulfonato and
pentafluorobenzenesulfonato; and sulfinato groups, such as methylsulfinato, phenylsulfinato,
benzylsulfinato, p-toluenesulfinato, trimethylbenzenesulfinato and pentafluorobenzenesulfinato.
[0155] Examples of the nitrogen-containing groups include amino group; alkylamino groups,
such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino and
dicyclohexylamino; and arylamino or alkylarylamino groups, such as phenylamino, diphenylamino,
ditolylamino, dinaphthylamino and methylphenylamino.
[0156] Examples of the phosphorus-containing groups include dimethylphosphino and diphenylphosphino.
[0157] Of these, R
11 is preferably a hydrocarbon group, particularly a hydrocarbon group of 1 to 3 carbon
atoms, i.e., methyl, ethyl or propyl.
[0158] R
12 is preferably hydrogen or a hydrocarbon group, particularly hydrogen or a hydrocarbon
group of 1 to 3 carbon atoms, i.e., methyl, ethyl or propyl.
R13 and R14
[0159] R
13 and R
14 are each an alkyl group of 1 to 20 carbon atoms, and examples thereof are the same
as those described above. R
13 is preferably a secondary or tertiary alkyl group. R
14 may contain a double bond or a triple bond.
X1 and X2
[0160] X
1 and X
2 may be the same as or different from each other and are each hydrogen, a halogen
atom, a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group
of 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group.
Examples of these groups are the same as those described above. X
1 and X
2 are each preferably a halogen atom or a hydrocarbon group of 1 to 20 carbon atoms.
Y
[0161] Y is a divalent hydrocarbon group of 1 to 20 carbon atoms, a divalent halogenated
hydrocarbon group of 1 to 20 carbon atoms, a divalent silicon-containing group, a
divalent germanium-containing group, a divalent tin-containing group, -O-, -CO-, -S-,
-SO-, -SO
2-, -NR
15-, -P(R
15)-, -P(O)(R
15)-, -BR
15- or -AlR
15- (The R
15 is hydrogen, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms or a halogenated
hydrocarbon group of 1 to 20 carbon atoms).
[0162] Examples of the divalent hydrocarbon groups of 1 to 20 carbon atoms include alkylene
groups, such as methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene,
1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene; and
arylalkylene groups, such as diphenylmethylene and diphenyl-1,2-ethylene.
[0163] Examples of the divalent halogenated hydrocarbon groups include those wherein the
above-exemplified divalent hydrocarbon groups of 1 to 20 carbon atoms are halogenated,
such as chloromethylene.
[0164] Examples of the divalent silicon-containing groups include alkylsilylene, alkylarylsilylene
and arylsilylene groups, such as methylsilylene, dimethylsilylene, diethylsilylene,
di(n-propyl)silylene, di(i-propyl)silylene, di(cyclohexyl)silylene, methylphenylsilylene,
diphenylsilylene, di(p-tolyl)silylene and di(p-chlorophenyl)silylene; and alkyldisilyl,
alkylaryldisilyl and aryldisilyl groups, such as tetramethyl-1,2-disilyl and tetraphenyl-1,2-disilyl.
[0165] Examples of the divalent germanium-containing groups include those wherein silicon
is replaced with germanium in the above-exemplified divalent silicon-containing groups.
[0166] R
15 is the same hydrogen, halogen atom, hydrocarbon group of 1 to 20 carbon atoms or
halogenated hydrocarbon group of 1 to 20 carbon atoms as described above.
[0167] Of these, Y is preferably a divalent silicon-containing group or a divalent germanium-containing
group, more preferably a divalent silicon-containing group, particularly preferably
an alkylsilylene group, an alkylarylsilylene group or an arylsilylene group.
[0168] Listed below are examples of the metallocene compounds represented by the formula
[C-a].
rac-Dimethylsilylene-bis(2,7-dimethyl-4-ethyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,7-dimethyl-4-n-propyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,7-dimethyl-4-i-propyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,7-dimethyl-4-n-butyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,7-dimethyl-4-sec-butyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,7-dimethyl-4-t-butyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,7-dimethyl-4-n-pentyl-1-indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis(2,7-dimethyl-4-n-hexyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,7-dimethyl-4-cyclohexyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,7-dimethyl-4-methylcyclohexyl-1-indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis(2,7-dimethyl-4-phenylethyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,7-dimethyl-4-phenyldichloromethyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,7-dimethyl-4-chloromethyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,7-dimethyl-4-trimethylsilylmethyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,7-dimethyl-4-trimethylsiloxymethyl-1-indenyl)zirconium
dichloride,
rac-Diethylsilylene-bis(2,7-dimethyl-4-i-propyl-1-indenyl)zirconium dichloride,
rac-Di(i-propyl)silylene-bis(2,7-dimethyl-4-i-propyl-1-indenyl)}zirconium dichloride,
rac-Di(n-butyl)silylene-bis(2,7-dimethyl-4-i-propyl-1-indenyl)zirconium dichloride,
rac-Di(cyclohexyl)silylene-bis(2,7-dimethyl-4-i-propyl-1-indenyl)zirconium dichloride,
rac-Methylphenylsilylene-bis(2,7-dimethyl-4-i-propyl-1-indenyl)zirconium dichloride,
rac-Methylphenylsilylene-bis(2,7-dimethyl-4-t-butyl-1-indenyl)zirconium dichloride,
rac-Diphenylsilylene-bis(2,7-dimethyl-4-t-butyl-1-indenyl)zirconium dichloride,
rac-Diphenylsilylene-bis(2,7-dimethyl-4-i-propyl-1-indenyl)zirconium dichloride,
rac-Diphenylsilylene-bis(2,7-dimethyl-4-ethyl-1-indenyl)zirconium dichloride,
rac-Di(p-tolyl)silylene-bis(2,7-dimethyl-4-i-propyl-1-indenyl)zirconium dichloride,
rac-Di(p-chlorophenyl)silylene-bis(2,7-dimethyl-4-i-propyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-i-propyl-7-ethyl-1-indenyl)zirconium dibromide,
rac-Dimethylsilylene-bis(2,3,7-trimethyl-4-ethyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,3,7-trimethyl-4-n-propyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,3,7-trimethyl-4-i-propyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,3,7-trimethyl-4-n-butyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,3,7-trimethyl-4-sec-butyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,3,7-trimethyl-4-t-butyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,3,7-trimethyl-4-n-pentyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,3,7-trimethyl-4-n-hexyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,3,7-trimethyl-4-cyclohexyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,3,7-trimethyl-4-methylcyclohexyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,3,7-trimethyl-4-trimethylsilylmethyl-1-indenyl)zirconium
dichloride,
rac-Dimethylsilylene-bis(2,3,7-trimethyl-4-trimethylsiloxymethyl-1-indenyl)zirconium
dichloride,
rac-Dimethylsilylene-bis(2,3,7-trimethyl-4-phenylethyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2,3,7-trimethyl-4-phenyldichloromethyl-1-indenyl)zirconium
dichloride,
rac-Dimethylsilylene-bis(2,3,7-trimethyl-4-chloromethyl-1-indenyl)zirconium dichloride,
rac-Diethylsilylene-bis(2,3,7-trimethyl-4-i-propyl-1-indenyl)zirconium dichloride,
rac-Di(i-propyl)silylene-bis(2,3,7-trimethyl-4-ipropyl-1-indenyl)zirconium dichloride,
rac-Di(n-butyl)silylene-bis(2,3,7-trimethyl-4-i-propyl-1-indenyl)zirconium dichloride,
rac-Di(cyclohexyl)silylene-bis(2,3,7-trimethyl-4-i-propyl-1-indenyl)zirconium dichloride,
rac-Methylphenylsilylene-bis(2,3,7-trimethyl-4-i-propyl-1-indenyl)zirconium dichloride,
rac-Methylphenylsilylene-bis(2,3,7-trimethyl-4-t-butyl-1-indenyl)zirconium dichloride,
rac-Diphenylsilylene-bis(2,3,7-trimethyl-4-t-butyl-1-indenyl)zirconium dichloride,
rac-Diphenylsilylene-bis(2,3,7-trimethyl-4-i-propyl-1-indenyl)zirconium dichloride,
rac-Diphenylsilylene-bis(2,3,7-trimethyl-4-ethyl-1-indenyl)zirconium dichloride,
rac-Di(p-tolyl)silylene-bis(2,3,7-trimethyl-4-i-propyl-1-indenyl)zirconium dichloride,
rac-Di(p-chlorophenyl)silylene-bis(2,3,7-trimethyl-4-i-propyl-1-indenyl)zirconium
dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconium dimethyl,
rac-Dimethylsilylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconium methylchloride,
rac-Dimethylsilylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconium-bis(methanesulfonato),
rac-Dimethylsilylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)zirconium-bis(p-phenylsulfinato),
rac-Dimethylsilylene-bis(2-methyl-3-methyl-4-i-propyl-7-methyl-1-indenyl)zirconium
dichloride,
rac-Dimethylsilylene-bis(2-ethyl-4-i-propyl-7-methyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-phenyl-4-i-propyl-7-methyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)titanium dichloride,
and
rac-Dimethylsilylene-bis(2-methyl-4-i-propyl-7-methyl-1-indenyl)hafnium dichloride.
[0169] Of these, particularly preferable are compounds having a branched alkyl group such
as i-propyl, sec-butyl or tert butyl at the 4-position.
[0170] In the invention, a racemic modification of the above-mentioned metallocene compound
is generally used as the olefin polymerization catalyst component, but R type or S
type is also employable.
[0171] The metallocene compounds can be synthesized from indene derivatives by known processes,
for example, a process described in Japanese Patent Laid-Open Publication No. 268307/1992.
[0172] In the present invention, a compound represented by the following formula [B-a],
which is described in European Patent No. 549,900 and Canadian Patent No. 2,084,017,
is also preferably employed.

[0173] In the formula [B-a], M is a transition metal atom of Group IVB of the periodic table,
specifically titanium, zirconium or hafnium, particularly preferably zirconium.
[0174] R
21s may be the same as or different from each other, and are each hydrogen, a halogen
atom, preferably fluorine or chlorine, an alkyl group of 1 to 10 carbon atoms, preferably
1 to 4 carbon atoms, which may be halogenated, an aryl group of 6 to 10 carbon atoms,
preferably 6 to 8 carbon atoms, -NR
2, -SR, -OSiR
3, -SiR
3 or -PR
2 (The R is a halogen atom, preferably chlorine, an alkyl group of 1 to 10 carbon atoms,
preferably 1 to 3 carbon atoms, or an aryl group of 6 to 10 carbon atoms, preferably
6 to 8 carbon atoms).
[0175] R
22 to R
28 may be the same as or different from each other, and are each the same atom or group
as described for R
21, and adjacent two or more groups out of R
22 to R
28 may form an aromatic or aliphatic ring together with an atom to which they are bonded.
[0176] X
3 and X
4 may be the same as or different from each other, and are each hydrogen, a halogen
atom, OH group, an alkyl group of 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms,
an alkoxy group of 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms, an aryl group
of 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, an aryloxy group of 6 to
10 carbon atoms, preferably 6 to 8 carbon atoms, an alkenyl group of 2 to 10 carbon
atoms, preferably 2 to 4 carbon atoms, an arylalkyl group of 7 to 40 carbon atoms,
preferably 7 to 10 carbon atoms, an alkylaryl group of 7 to 40 carbon atoms, preferably
7 to 12 carbon atoms, or an arylalkenyl group of 8 to 40 carbon atoms, preferably
8 to 12 carbon atoms.
[0177] Z is

=BR
29, =AlR
29, -Ge, -Sn-, -O-, -S-, =SO, =SO
2, =NR
29, =CO, =PR
29 or =p(O)R
29.
[0178] In the above formulas, R
29 and R
30 may be the same as or different from each other and are each hydrogen, a halogen
atom, an alkyl group of 1 to 10 carbon atom, preferably 1 to 4 carbon atoms, particularly
preferably methyl, a fluoroalkyl group of 1 to 10 carbon atoms, preferably CF
3, an aryl group of 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, a fluoroaryl
group of 6 to 10 carbon atoms, preferably pentafluorophenyl, an alkoxy group of 1
to 10 carbon atoms, preferably 1 to 4 carbon atoms, particularly preferably methoxy,
an alkenyl group of 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms, an arylalkyl
group of 7 to 40 carbon atoms, preferably 7 to 10 carbon atoms, an arylalkenyl group
of 8 to 40 carbon atoms, preferably 8 to 12 carbon atoms, or an alkylaryl group of
7 to 40 carbon atoms, preferably 7 to 12 carbon atoms.
[0179] R
29 and R
30 may form a ring together with an atom to which they are bonded.
[0180] M
2 is silicon, germanium or tin.
[0181] The alkyl group is a straight chain or branched alkyl group, and the halogen (for
halogenation) is fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine.
[0182] Of the compounds of the formula [B-a], preferable are those wherein M is zirconium
or hafnium; R
21s are the same as each other, and are each an alkyl group of 1 to 4 carbon atoms;
R
22 to R
28 may be the same as or different from each other, and are each hydrogen or an alkyl
group of 1 to 4 carbon atoms; X
3 and X
4 may be the same as or different from each other, and are each an alkyl group of 1
to 3 carbon atoms or a halogen atom; and Z preferably is

(M
2 is silicon, and R
29 and R
30 may be the same as or different from each other and are each an alkyl group of 1
to 4 carbon atom or an aryl group of 6 to 10 carbon atoms).
[0183] Among such compounds, more preferable are those wherein the substituents R
22 and R
28 are each hydrogen, and R
23 to R
27 are each an alkyl group of 1 to 4 carbon atoms or hydrogen.
[0184] Still more preferable are compounds wherein M is zirconium; R
21s are the same as each other and are each an alkyl group of 1 to 4 carbon atoms; R
22 and R
28 are each hydrogen; R
23 to R
27 may be the same as or different from each other, and are each an alkyl group of 1
to 4 carbon atoms or hydrogen; X
3 and X
4 are each chlorine; and Z preferably is

(M
2 is silicon, and R
29 and R
30 may be the same as or different from each other and are each an alkyl group of 1
to 4 carbon atom or an aryl group of 6 to 10 carbon atoms).
[0185] Particularly preferable are compounds wherein M is zirconium; R
21s are each methyl; R
22 to R
28 are each hydrogen; X
3 and X
4 are chlorine; and Z preferably is

(M
2 is silicon, and R
29 and R
30 may be the same as or different from each other and are each methyl or phenyl).
[0186] Listed below are some examples of the compounds represented by the formula [B-a].
rac-Dimethylsilylene-bis{1-(2-methyl-4,5-benzoindenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-methyl-4,5-acenaphthocyclopentadienyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2,3,6-trimethyl-4,5-benzoindenyl)}zirconium dichloride,
rac-Methylphenylsilylene-bis{1-(2-methyl-4,5-benzoindenyl)}zirconium dichloride,
rac-Methylphenylsilylene-bis{1-(2-methyl-4,5-acenaphthocyclopentadienyl)}zirconium
dichloride,
rac-Methylphenylsilylene-bis{1-(4,5-benzoindenyl)}zirconium dichloride,
rac-Methylphenylsilylene-bis{1-(2,6-dimethyl-4,5-benzoindenyl)}zirconium dichloride,
and
rac-Methylphenylsilylene-bis{1-(2,3,6-trimethyl-4,5-benzoindenyl)}zirconium dichloride.
[0187] Also employable are compounds wherein zirconium is replaced with titanium or hafnium
in the above-exemplified compounds.
[0188] In the invention, a racemic modification of the metallocene compound represented
by the formula [C-a] or [B-a] is generally used as the olefin polymerization catalyst
component, but R type or S type is also employable.
[0189] The metallocene compounds mentioned above can be used in combination of two or more
kinds.
[0190] The metallocene compound [a] employable for preparing the long-chain branched ethylene/α-olefin
copolymer rubber that is preferably used in the invention is, for example, a compound
represented by the following formula [II].

[0191] In the formula [II], M is a transition metal atom of Group IVB of the periodic table,
specifically titanium, zirconium or hafnium, particularly preferably zirconium.
Substituent R1
[0192] R
1 is a hydrocarbon group of 1 to 6 carbon atoms, and examples thereof include alkyl
groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,
tert-butyl, n-pentyl, neopentyl, n-hexyl and cyclohexyl; and alkenyl groups, such
as vinyl and propenyl.
[0193] Of these, preferable are alkyl groups whose carbon bonded to the indenyl group is
primary carbon. More preferable are alkyl groups of 1 to 4 carbon atoms, and particularly
preferred are methyl and ethyl.
Substituents R2, R4, R5 and R6
[0194] R
2, R
4, R
5 and R
6 may be the same as or different from each other and are each hydrogen, a halogen
atom or the same hydrocarbon group of 1 to 6 carbon atoms as described for R
1.
[0195] The halogen atom is fluorine, chlorine, bromine or iodine.
Substituent R3
[0196] R
3 is an aryl group of 6 to 16 carbon atoms. This aryl group may be substituted with
a halogen atom, a hydrocarbon group of 1 to 2C carbon atoms or an organosilyl group.
[0197] Examples of the aryl groups include phenyl, α-naphthyl, β-naphthyl, anthracenyl,
phenanthryl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl,
indanyl and biphenylyl. Of these, phenyl, naphthyl, anthracenyl and phenanthryl are
preferable.
[0198] Examples of the hydrocarbon groups of 1 to 20 carbon atoms serving as substituents
of the aryl groups include:
alkyl groups, such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl,
dodecyl, eicosyl, norbornyl and adamantyl;
alkenyl groups, such as vinyl, propenyl and cyclohexenyl;
arylalkyl groups, such as benzyl, phenylethyl and phenylpropyl; and
aryls groups, such as the above-exemplified aryl groups, tolyl, dimethylphenyl, trimethylphenyl,
ethylphenyl, propylphenyl, methylnaphthyl and benzylphenyl.
[0199] Examples of the organosilyl groups include trimethylsilyl, triethylsilyl and triphenylsilyl.
X1 and X2
[0200] X
1 and X
2 are each hydrogen, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms which
may be substituted with halogen, an oxygen-containing group or a sulfur-containing
group. Examples of the halogen atoms and the hydrocarbon groups are the same as those
mentioned above.
[0201] Examples of the oxygen-containing groups include hydroxyl group; alkoxy groups, such
as methoxy, ethoxy, propoxy and butoxy; aryloxy groups, such as phenoxy, methylphenoxy,
dimethylphenoxy and naphthoxy; and arylalkoxy groups, such as phenylmethoxy and phenylethoxy.
[0202] Examples of the sulfur-containing groups include substituents wherein oxygen is replaced
with sulfur in the above-exemplified oxygen-containing groups; sulfonato groups, such
as methylsulfonato, trifluoromethanesulfonato, phenylsulfonato, benzylsulfonato, p-toluenesulfonato,
trimethylbenzenesulfonato, triisobutylbenzenesulfonato, p-chlorobenzenesulfonato and
pentafluorobenzenesulfonato; and sulfinato groups, such as methylsulfinato, phenylsulfinato,
benzenesulfinato, p-toluenesulfinato, trimethylbenzenesulfinato and pentafluorobenzenesulfinato.
[0203] Of these, X
1 and X
2 are each preferably a halogen atom or a hydrocarbon group of 1 to 20 carbon atoms.
Y
[0204] Y is a divalent hydrocarbon group of 1 to 20 carbon atoms, a divalent halogenated
hydrocarbon group of 1 to 20 carbon atoms, a divalent silicon-containing group, a
divalent germanium-containing group, -O-, -CO-, -S-, -SO-, -SO
2-, -NR
7-, -P(R
7)-, -P(O)(R
7)-, -BR
7- or -AlR
7- (The R
7 is hydrogen, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms or a halogenated
hydrocarbon group of 1 to 20 carbon atoms).
[0205] Examples of the divalent hydrocarbon groups of 1 to 20 carbon atoms include alkylene
groups, such as methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene,
1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene; and
arylalkylene groups, such as diphenylmethylene and diphenyl-1,2-ethylene.
[0206] Examples of the divalent halogenated hydrocarbon groups include those wherein the
above-exemplified divalent hydrocarbon groups of 1 to 20 carbon atoms are halogenated,
such as chloromethylene.
[0207] Examples of the divalent silicon-containing groups include alkylsilylene, alkylarylsilylene
and arylsilylene groups, such as methylsilylene, dimethylsilylene, diethylsilylene,
di(n-propyl) silylene, di(i-propyl)silylene, di(cyclohexyl)silylene, methylphenylsilylene,
diphenylsilylene, di(p-tolyl)silylene and di(p-chlorophenyl)silylene; and alkyldisilyl,
alkylaryldisilyl and aryldisilyl groups, such as tetramethyl-1,2-disilyl and tetraphenyl-1,2-disilyl.
[0208] Examples of the divalent germanium-containing groups include those wherein silicon
is replaced with germanium in the above-exemplified divalent silicon-containing groups.
[0209] R
7 is the same halogen atom, hydrocarbon group of 1 to 20 carbon atoms or halogenated
hydrocarbon group of 1 to 20 carbon atoms as described above.
[0210] Of these, Y is preferably a divalent silicon-containing group or a divalent germanium-containing
group, more preferably a divalent silicon-containing group, particularly preferably
an alkylsilylene group, an alkylarylsilylene group or an arylsilylene group.
[0211] Listed below are examples of the metallocene compounds represented by the above formula
[II].
rac-Dimethylsilylene-bis(4-phenyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-methyl-4-phenylindenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(α-naphthyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(β-naphthyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(1-anthracenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(2-anthracenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(9-anthracenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(9-phenanthryl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(p-fluorophenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(pentafluorophenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(p-chlorophenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(m-chlorophenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(o-chlorophenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(o,p-dichlorophenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(p-bromophenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(p-tolyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(m-tolyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(o-tolyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(o,o'-dimethylphenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(p-ethylphenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(p-i-propylphenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(p-benzylphenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(p-biphenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(m-biphenyl)-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(p-trimethylsilylenephenyl)-1-indenyl)zirconium
dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-(m-trimethylsilylenephenyl)-1-indenyl)zirconium
dichloride,
rac-Dimethylsilylene-bis(2-phenyl-4-phenyl)-1-indenyl)zirconium dichloride,
rac-Diethylsilylene-bis(2-methyl-4-phenyl)-1-indenyl)zirconium dichloride,
rac-Di(i-propyl)silylene-bis(2-methyl-4-phenyl-1-indenyl)}zirconium dichloride,
rac-Di(n-butyl)silylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride,
rac-Dicyclohexylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride,
rac-Methylphenylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride,
rac-Diphenylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride,
rac-Di(p-tolyl)silylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride,
rac-Di(p-chlorophenyl)silylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride,
rac-Methylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride,
rac-Ethylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride,
rac-Dimethylgermylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride,
rac-Dimethylstannylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride,
rac-Dimethylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium dibromide,
rac-Dimethylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium dimethyl,
rac-Dimethylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium methylchloride,
rac-Dimethylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium chloride SO2Me,
rac-Dimethylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconium chloride OSO2Me,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(α-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(β-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(2-methyl-1-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(5-acenaphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(9-anthracenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(9-phenanthryl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(o-methylphenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(m-methylphenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(p-methylphenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(2,3-dimethylphenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(2,4-dimethylphenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(2,5-dimethylphenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(2,4,6-trimethylphenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(o-chlorophenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(m-chlorophenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(p-chlorophenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(2,3-dichlorophenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(2,6-dichlorophenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(3,5-dichlorophenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(2-bromophenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(3-bromophenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(4-bromophenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(4-biphenylyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-ethyl-4-(4-trimethylsilylphenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-propyl-4-phenylindenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-propyl-4-(α-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-propyl-4-(β-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-propyl-4-(2-methyl-1-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-propyl-4-(5-acenaphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-propyl-4-(9-anthracenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-propyl-4-(9-phenanthryl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-i-propyl-4-phenylindenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-i-propyl-4-(α-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-i-propyl-4-(β-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-i-propyl-4-(8-methyl-9-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-i-propyl-4-(5-acenaphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-i-propyl-4-(9-anthracenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-i-propyl-4-(9-phenanthryl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-s-butyl-4-phenylindenyl)}zirconium, dichloride,
rac-Dimethylsilylene-bis{1-(2-s-butyl-4-(α-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-s-butyl-4-(β-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-s-butyl-4-(2-methyl-1-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-s-butyl-4-(5-acenaphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-s-butyl-4-(9-anthracenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-s-butyl-4-(9-phenanthryl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-pentyl-4-phenylindenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-pentyl-4-(α-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-butyl-4-phenylindenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-butyl-4-(α-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-butyl-4-(β-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-butyl-4-(2-methyl-1-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-butyl-4-(5-acenaphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-butyl-4-(9-anthracenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-butyl-4-(9-phenanthryl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-i-butyl-4-phenylindenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-i-butyl-4-(α-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-i-butyl-4-(β-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-i-butyl-4-(2-methyl-1-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-i-butyl-4-(5-acenaphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-i-butyl-4-(9-anthracenyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-i-butyl-4-(9-phenanthryl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-neopentyl-4-phenylindenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-neopentyl-4-(α-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-hexyl-4-phenylindenyl)}zirconium dichloride,
rac-Dimethylsilylene-bis{1-(2-n-hexyl-4-(α-naphthyl)indenyl)}zirconium dichloride,
rac-Methylphenylsilylene-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride,
rac-Methylphenylsilylene-bis{1-(2-ethyl-4-(α-naphthyl)indenyl)}zirconium dichloride,
rac-Methylphenylsilylene-bis{1-(2-ethyl-4-(9-anthracenyl)indenyl)}zirconium dichloride,
rac-Methylphenylsilylene-bis{1-(2-ethyl-4-(9-phenanthryl)indenyl)}zirconium dichloride,
rac-Diphenylsilylene-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride,
rac-Diphenylsilylene-bis{1-(2-ethyl-4-(α-naphthyl)indenyl)}zirconium dichloride,
rac-Diphenylsilylene-bis{1-(2-ethyl-4-(9-anthracenyl)indenyl)}zirconium dichloride,
rac-Diphenylsilylene-bis{1-(2-ethyl-4-(9-phenanthryl)indenyl)}zirconium dichloride,
rac-Diphenylsilylene-bis{1-(2-ethyl-4-(4-biphenylyl)indenyl)}zirconium dichloride,
rac-Methylene-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride,
rac-Methylene-bis{1-(2-ethyl-4-(α-naphthyl)indenyl)}zirconium dichloride,
rac-Ethylene-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride,
rac-Ethylene-bis{1-(2-ethyl-4-(α-naphthyl)indenyl)}zirconium dichloride,
rac-Ethylene-bis{1-(2-n-propyl-4-(α-naphthyl)indenyl)}zirconium dichloride,
rac-Dimethylgermyl-bis{1-(2-ethyl-4-phenylindenyl)}zirconium dichloride,
rac-Dimethylgermyl-bis{1-(2-ethyl-4-(α-naphthyl)indenyl)}zirconium dichloride, and
rac-Dimethylgermyl-bis{1-(2-n-propyl-4-phenylindenyl)}zirconium dichloride.
[0212] Also employable are compounds wherein zirconium is replaced with titanium or hafnium
in the above-exemplified compounds.
[0213] In the invention, a racemic modification of the metallocene compound is generally
used as the catalyst component, but R type or S type is also employable.
[0214] The metallocene compounds mentioned above can be used in combination of two or more
kinds.
[0215] The metallocene compounds can be prepared in accordance with "Journal of Organometallic
Chem.", 288 (1985), pp. 63-67 and European Patent Application No. 0,320,762.
[0216] Other than the metallocene compound of the formula [II], a compound represented by
the following formula [III] is also employable.
L
aMX
2 [III]
wherein M is a metal of Group IV of the periodic table or a metal of lanthanide series;
La is a derivative of delocalization π bond group and imparts restraint geometrical
shape to the metal M active site; and
Xs are each independently hydrogen, a halogen atom, a hydrocarbon group containing
20 or less carbon atoms, silicon or germanium, a silyl group or a germyl group.
[0217] Of the compounds of the formula [III], preferable are those represented by the following
formula [III-a].

[0218] In the formula [III-a], M is titanium, zirconium or hafnium, and X is the same as
described above.
[0219] Cp is π-bonded to M and is a substituted cyclopentadienyl group having a substituent
Z or its derivative.
[0220] Z is oxygen, sulfur, boron or an element of Group IVA of the periodic table (for
example, silicon, germanium or tin).
[0221] Y is a ligand containing nitrogen, phosphorus, oxygen or sulfur.
[0222] Z and Y may together form a condensed ring.
[0223] Listed below are examples of the compounds represented by the formula [III-a].
(Dimethyl(t-butylamide) (tetramethyl-η5-cyclopentadienyl)silane)titanium dichloride,
((t-Butylamide)(tetramethyl-η5-cyclopentadienyl)-1,2-ethanediyl)titanium dichloride,
(Dibenzyl (t-butylamide) (tetramethyl-η5-cyclopentadienyl)silane)titanium dichloride,
(Dimethyl(t-butylamide) (tetramethyl-η5-cyclopentadienyl)silane)dibenzyltitanium,
(Dimethyl(t-butylamide) (tetramethyl-η5-cyclopentadienyl)silane)dimethyltitanium,
((t-Butylamide) (tetramethyl-η5-cyclopentadienyl)-1,2-ethanediyl)dibenzyltitanium,
((Methylamide) (tetramethyl-η5-cyclopentadienyl)-1,2-ethanediyl)dineopentyltitanium,
((Phenylphosphide) (tetramethyl-η5-cyclopentadienyl)-methylene)diphenyltitanium,
(Dibenzyl(t-butylamide) (tetramethyl-η5-cyclopentadienyl)silane)dibenzyltitanium,
(Dimethyl(benzylamide) (η5-cyclopentadienyl)silane)di(trimethylsilyl)titanium,
(Dimethyl(phenylphosphide)-(tetramethyl-η5-cyclopentadienyl)silane)dibenzyltitanium,
(Tetramethyl-η5-cyclopentadienyl)-1,2-ethanediyl)dibenzyltitanium,
(2-η5-(Tetramethyl-cyclopentadienyl)-1-methyl-ethanolate(2-))dibenzyltitanium,
(2-η5-(Tetramethyl-cyclopentadienyl)-1-methyl-ethanolate(2-))dimethyltitanium,
(2-((4a,4b,8a,9,9a-η)-9H-Fluorene-9-yl)cyclohexanolate(2-))dimethyltitanium, and
(2-((4a,4b,8a,9,9a-η)-9H-Fluorene-9-yl)cyclohexanolate(2-))dibenzyltitanium.
[0224] In the invention, the metallocene compounds represented by the formula [III] can
be used in combination of two or more kinds.
[0225] Some of titanium compounds are listed above as examples of the metallocene compounds,
but compounds wherein titanium is replaced with zirconium or hafnium in the above-exemplified
titanium compounds are also employable.
[0226] These compounds may be used alone or in combination of two or more kinds.
[0227] Of the above-mentioned various metallocene compounds, the metallocene compound represented
by the formula [II] is preferably used in the preparation of the long-chain branched
ethylene/α-olefin copolymer rubber.
Organoaluminum oxy-compound [b]
[0228] The organoaluminum oxy-compound [b] used in the invention may be aluminoxane conventionally
known or a benzene-insoluble organoaluminum oxy-compound exemplified in Japanese Patent
Laid-Open Publication No. 78687/1990.
[0229] The conventionally known aluminoxane can be prepared by, for example, the following
procedures.
(1) An organoaluminum compound such as trialkylaluminum is added to a hydrocarbon
medium suspension of compounds containing adsorbed water or salts containing water
of crystallization, e.g., magnesium chloride hydrate, copper sulfate hydrate, aluminum
sulfate hydrate, nickel sulfate hydrate or cerous chloride hydrate, so as to allow
the organoaluminum compound to react with the compound or the salt, followed by recovering
aluminoxane as its hydrocarbon solution.
(2) water, ice or water vapor is allowed to directly act on an organoaluminum compound
such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran,
followed by recovering aluminoxane as its hydrocarbon solution.
(3) An organotin oxide such as dimethyltin oxide or dibutyltin oxide is allowed to
react with an organoaluminum compound such as trialkylaluminum in a medium such as
decane, benzene or toluene.
[0230] The aluminooxane may contain a small amount of an organometallic component. Further,
it is possible that the solvent or the unreacted organoaluminum compound is distilled
off from the recovered solution of aluminooxane and that the remainder is redissolved
in a solvent.
[0231] Examples of the organoaluminum compounds used for preparing the aluminoxane include:
trialkylaluminums, such as trimethylaluminum, triethylaluminum, tripropylaluminum,
triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum,
tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum and
tridecylaluminum;
tricycloalkylaluminums, such as tricyclohexylaluminum and tricyclooctylaluminum;
dialkylaluminum halides, such as dimethylaluminum chloride, diethylaluminum chloride,
diethylaluminum bromide and diisobutylaluminum chloride;
dialkylaluminum hydrides, such as diethylaluminum hydride and diisobutylaluminum hydride;
dialkylaluminum alkoxides, such as dimethylaluminum methoxide and diethylaluminum
ethoxide; and
dialkylaluminum aryloxides, such as diethylaluminum phenoxide.
[0232] Of these, particularly preferable are trialkylaluminums and tricycloalkylaluminums.
[0233] Also employable as the organoaluminum compound used for preparing the aluminoxane
is isoprenylaluminum represented by the formula (i-C
4H
9)
xAl
y(C
5H
10)
z (wherein x, y, z are each a positive number, and z ≥ 2x).
[0234] The organoaluminum compounds mentioned above can be used in combination of two or
more kinds.
[0235] Examples of the solvents used for preparing the aluminoxane include:
aromatic hydrocarbons, such as benzene, toluene, xylene, cumene and cymene;
aliphatic hydrocarbons, such as pentane, hexane, heptane, octane, decane, dodecane,
hexadecane and octadecane;
alicyclic hydrocarbons, such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane;
petroleum fractions, such as gasoline, kerosine and gas oil; and
halides of these aromatic, aliphatic and alicyclic hydrocarbons, particularly chlorides
and bromides thereof.
[0236] Also employable are ethers such as ethyl ether and tetrahydrofuran.
[0237] Of the solvents, particularly preferable are aromatic hydrocarbons.
Compound [c] which reacts with the metallocene compound [a] to form an ion pair
[0238] The compound [c] which reacts with the metallocene compound [a] to form an ion pair
includes Lewis acid, ionic compounds, borane compounds and carborane compounds described
in National Publications of international Patent No. 501950/1989 and No. 502036/1989,
Japanese Patent Laid-Open Publication No. 179005/1991, No. 179006/1991, No. 207703/1991
and No. 207704/1991, and U.S. Patent No. 5,321,106.
[0239] The Lewis acid includes Mg-containing Lewis acid, Al-containing Lewis acid and B-containing
Lewis acid. Of these, B-containing Lewis acid is preferred.
[0240] The Lewis acid which contains a boron atom is, for example, a compound represented
by the following formula:
BR
1R
2R
3
wherein R
1, R
2 and R
3 are each independently a phenyl group which may have a substituent such as fluorine,
methyl or trifluoromethyl, or a fluorine atom.
[0241] Examples of the compounds represented by the above formula include trifluoroboron,
triphenylboron, tris(4-fluorophenyl)boron, tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron,
tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron and tris(3,5-dimethylphenyl)boron.
Of these, particularly preferred is tris(pentafluorophenyl)boron.
[0242] The ionic compound employable in the invention is a salt comprising a cationic compound
and an anionic compound. The anion reacts with the metallocene compound [a] to render
the compound [a] cationic and to form an ion pair, thereby to stabilize the transition
metal cation seed. Examples of such anions include organoboron compound anion, organoarsenic
compound anion and organoaluminum compound anion. Preferable are anions which are
relatively bulky and stabilize the transition metal cation seed. Examples of the cations
include metallic cation, organometallic cation, carbonium cation, tripium cation,
oxonium cation, sulfonium cation, phosphonium cation and ammonium cation. More specifically,
there can be mentioned triphenylcarbenium cation, tributylammonium cation, N,N-dimethylammonium
cation, ferrocenium cation, etc.
[0243] In the invention, ionic compounds containing an organoboron compound anion are preferred,
and examples thereof include:
trialkyl-substituted ammonium salts, such as triethylammoniumtetra(phenyl)boron, tripropylammoniumtetra(phenyl)boron,
tri(n-butyl)ammoniumtetra(phenyl)boron, trimethylammoniumtetra(p-tolyl)boron, trimethylammoniumtetra(o-tolyl)boron,
tributylammoniumtetra(pentafluorophenyl)boron, tripropylammoniumtetra(o,p-dimethylphenyl)boron,
tributylammoniumtetra(m,m-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron,
tri(n-butyl)ammoniumtetra(o-tolyl)boron and tri(n-butyl)ammoniumtetra(4-fluorophenyl)boron;
N,N,-dialkylanilinium salts, such as N,N-dimethylaniliniumtetra(phenyl)boron, N,N-diethylaniliniumtetra(phenyl)boron
and N,N-2,4,6-pentamethylaniliniumtetra(phenyl)boron;
dialkylammonium salts, such as di(n-propyl)ammoniumtetra(pentafluorophenyl)boron and
dicyclohexylammoniumtetra(phenyl)boron; and
triarylphosphonium salts, such as triphenylphosphoniumtetra(phenyl)boron, tri(methylphenyl)phosphoniumtetra(phenyl)boron
and tri(dimethylphenyl)phosphoniumtetra(phenyl)boron.
[0244] As the ionic compounds containing a boron atom, triphenylcarbeniumtetrakis(pentafluorophenyl)borate,
N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate and ferroceniumtetrakis(pentafluorophenyl)borate
are also employable in the invention.
[0245] Further, the following ionic compounds containing a boron atom are also employable.
(In the ionic compounds enumerated below, the counter ion is tri(n-butyl)ammonium,
but the counter ion is in no way limited thereto.)
[0246] That is, there can be mentioned salts of anion, for example, bis[tri(n-butyl)ammonium]nonaborate,
bis[tri(n-butyl)ammonium]decaborate, bis[tri(n-butyl)ammonium] undecaborate, bis[tri(n-butyl)ammonium]dodecaborate,
bis[tri(n-butyl)ammonium]decachlorodecaborate, bis[tri(n-butyl)ammonium]dodecachlorododecaborate,
tri(n-butyl)ammonium-1-carbadecaborate, tri(n-butyl)ammonium-1-carbaundecaborate,
tri(n-butyl)amnonium-1-carbadodecaborate, tri(n-butyl)ammonium-1-trimethylsilyl-1-carbadecaborate
and tri(n-butyl)ammoniumbromo-1-carbadodecaborate.
[0247] Moreover, borane compounds and carborane compounds are also employable. These compounds
are used as the Lewis acid or the ionic compounds.
[0248] Examples of borane compounds, carborane complex compounds and salts of carborane
anions include decaborane(14), 7,8-dicarbaundecaborane(13), 2,7-dicarbaundecaborane(13),
undecahydride-7,8-dimethyl-7,8-dicarbaundecaborane, dodecahydride-11-methyl-2,7-dicarbaundecaborane,
tri(n-butyl)ammonium-6-carbadecaborate(l4), tri(n-butyl)ammonium-6-carbadecaborate(12),
tri(n-butyl)ammonium-7-carbaundecaborate(13), tri(n-butyl)ammonium-7,8-dicarbaundecaborate(12),
tri(n-butyl)ammonium-2,9-dicarbaundecaborate(12), tri(n-butyl)ammoniumdodecahydride-8-methyl-7,9-dicarbaundecaborate,
tri(n-butyl)ammoniumundecahydride-8-ethyl-7,9-dicarbaundecaborate, tri(n-butyl)ammoniumundecahydride-8-butyl-7,9-dicarbaundecaborate,
tri(n-butyl)ammoniumundecahydride-8-allyl-7,9-dicarbaundecaborate, tri(n-butyl)ammoniumundecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate
and tri(n-butyl)ammoniumundecahydride-4,6-dibromo-7-carbaundecaborate.
[0249] Examples of carborane compounds and salts of carboranes include 4-carbanonaborane(14),
1,3-dicarbanonaborane(13), 6,9-dicarbadecaborane(14), dodecahydride-1-phenyl-1,3-dicarbanonaborane,
dodecahydride-1-methyl-1,3-dicarbanonaborane and undecahydride-1,3-dimethyl-1,3-dicarbanonaborane.
[0250] Furthermore, the following compounds are also employable. (In the ionic compounds
enumerated below, the counter ion is tri(n-butyl)ammonium, but the counter ion is
in no way limited thereto.)
[0251] That is, there can be mentioned salts of metallic carboranes and metallic borane
anions, for example, tri(n-butyl)ammoniumbis(nonahydride-1,3-dicarbanonaborate)cobaltate
(III), tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)ferrate(III),
tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)cobaltate(III), tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)nickelate(III),
tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)cuprate(III), tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)aurate(III),
tri(n-butyl)ammoniumbis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate)ferrate(III),
tri(n-butyl)ammoniumbis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate)chromate(III),
tri(n-butyl)ammoniumbis(tribromooctahydride-7,8-dicarbaundecaborate)cobaltate(III),
tri(n-butyl)ammoniumbis(dodecahydridedicarbadodecaborate)-cobaltate(III), bis[tri(n-butyl)ammonium]bis(dodecahydridedodecaborate)-nickelate(III),
tris[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)chromate(III), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)manganate(IV),
bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)cobaltate(III) and
bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)nickelate(IV).
[0252] The compounds [c] mentioned above can be used singly or in combination of two or
more kinds.
Organoaluminum compound [d]
[0253] The organoaluminum compound [d] used in the invention can be represented by, for
example, the following general formula (a) :
R
5 nAlX
3-n (a)
wherein R
5 is a hydrocarbon group of 1 to 12 carbon atoms, X is a halogen atom or hydrogen,
and n is 1 to 3.
[0254] In the formula (a), R
5 is a hydrocarbon group of 1 to 12 carbon atoms, e.g., an alkyl group, a cycloalkyl
group or an aryl group. Examples of such groups include methyl, ethyl, n-propyl, isopropyl,
isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl and tolyl.
[0255] Examples of such organoaluminum compounds include:
trialkylaluminums, such as trimethylaluminum, triethylaluminum, triisopropylaluminum,
triisobutylaluminum, trioctylaluminum and tri-2-ethylhexylaluminum;
alkenylaluminums, such as isoprenylaluminum;
dialkylaluminum halides, such as dimethylaluminum chloride, diethylaluminum chloride,
diisopropylaluminum chloride, diisobutylaluminum chloride and dimethylaluminum bromide;
alkylaluminum sesquihalides, such as methylaluminum sesquichloride, ethylaluminum
sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride and
ethylaluminum sesquibromide;
alkylaluminum dihalides, such as methylaluminum dichloride, ethylaluminum dichloride,
isopropylaluminum dichloride and ethylaluminum dibromide; and
alkylaluminum hydrides, such as diethylaluminum hydride and diisobutylaluminum hydride.
[0256] Also employable as the organoaluminum compound [d] is a compound represented by the
following formula (b) :
R
5 nAlY
3-n (b)
wherein R
5 is the same as R
5 in the formula (a); Y is -OR
6 group, -OSiR
73 group, -OAlR
82 group, -NR
92 group, -SiR
103 group or -N(R
11)AlR
122 group; n is 1 to 2; R
6, R
7, R
8 and R
12 are each methyl, ethyl, isopropyl, isobutyl, cyclohexyl, phenyl or the like; R
9 is hydrogen, methyl, ethyl, isopropyl, phenyl, trimethylsilyl or the like; and R
10 and R
11 are each methyl, ethyl or the like.
[0257] Examples of such organoaluminum compounds include:
(i) compounds of the formula R5nAl(OR6)3-n, e.g., dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum
methoxide;
(ii) compounds of the formula R5nAl (OSiR73)3-n, e.g., (C2H5)2Al(OSi(CH3)3), (iso-C4H9)2Al(OSi(CH3)3) and (iso-C4H9)2Al(OSi(C2H5)3);
(iii) compounds of the formula R5nAl(OAlR82)3-n, e.g., (C2H5)2Al(OAl(C2H5)2) and (iso-C4H9)2Al(OAl(iso-C4H9)2);
(iv) compounds of the formula R5nAl(NR92)3-n, e.g., (CH3)2Al(N(C2H5)2), (C2H5)2Al(NH(CH3)), (CH3)2Al(NH(C2H5)), (C2H5)2Al[N(Si(CH3)3)2] and (iso-C4H9)2Al[N(Si(CH3)3)2]; and
(v) compounds of the formula R5nAl(SiR103)3-n, e.g., (iso-C4H9)2Al(Si(CH3)3).
[0258] Of these, preferable are organoaluminum compounds of the formulae R
53Al, R
5nAl(OR
6)
3-n and R
5nAl(OAlR
82)
3-n, and particularly preferred are compounds of said formulae wherein R
5 is an isoalkyl group and n is 2. The organoaluminum compounds mentioned above can
be used in combination of two or more kinds.
[0259] The specific metallocene catalyst employable in the invention contains the metallocene
compound [a], and the catalyst can be formed from, for example, the metallocene compound
[a] and the organoaluminum oxy-compound [b] as mentioned above. The metallocene catalyst
may be formed from the metallocene compound [a] and the compound [c] which reacts
with the compound [a] to form an ion pair, or it may be formed from the metallocene
compound [a], the organoaluminum oxy-compound [b] and the compound [c] which forms
an ion pair. In these embodiments, it is particularly preferable to further use the
organoaluminum compound [d] in combination.
[0260] In the present invention, the metallocene compound [a] is used in an amount of usually
about 0.00005 to 0.1 mmol, preferably about 0.0001 to 0.05 mmol, in terms of the transition
metal atom, based on 1 liter of the polymerization volume.
[0261] The organoaluminum oxy-compound [b] is used in such an amount that the amount of
the aluminum atom becomes usually about 1 to 10,000 mol, preferably 10 to 5,000 mol,
per 1 mol of the transition metal atom.
[0262] The compound [c] which reacts with the metallocene compound [a] to form an ion pair
is used in such an amount that the amount of the boron atom becomes usually about
0.5 to 20 mol, preferably 1 to 10 mol, based on 1 mol of the transition metal atom.
[0263] The organoaluminum compound [d] is used optionally in an amount of usually about
0 to 1,000 mol, preferably about 0 to 500 mol, based on 1 mol of the aluminum atom
in the organoaluminum oxy-compound [b] or the boron atom in the compound [c] which
forms an ion pair.
[0264] When ethylene and the α-olefin of 6 to 20 carbon atoms are copolymerized using such
a metallocene catalyst as mentioned above, a linear or long-chain branched ethylene/α-olefin
random copolymer can be obtained with high polymerization activities.
[0265] However, even if ethylene and the α-olefin of 6 to 20 carbon atoms are copolymerized
using a Group VB transition metal compound catalyst such as a vanadium catalyst, a
linear or long-chain branched ethylene/α-olefin random copolymer cannot be obtained
with sufficient polymerization activities.
[0266] In the copolymerization of ethylene and the α-olefin of 6 to 20 carbon atoms, the
metallocene compound [a], the organoaluminum oxy-compound [b] and the ion pair-forming
compound [c], and optionally, the organoaluminum compound [d], all of which constitute
the metallocene catalyst, may be separately fed to the polymerization reactor, or
a preliminarily prepared metallocene catalyst containing the metallocene compound
[a] may be added to the polymerization reaction system.
[0267] In the preparation of the metallocene catalyst, hydrocarbon solvents which are inert
to the catalyst components can be employed. Examples of the inert hydrocarbon solvents
include aliphatic hydrocarbons, such as propane, butane, pentane, hexane, heptane,
octane, decane, dodecane and kerosine; alicyclic hydrocarbons, such as cyclopentane,
cyclohexane and methylcyclopentane; aromatic hydrocarbons, such as benzene, toluene
and xylene; and halogenated hydrocarbons, such as ethylene chloride, chlorobenzene
and dichloromethane. These hydrocarbon solvents can be used singly or in combination.
[0268] The metallocene compound [a], the organoaluminum oxy-compound [b], the ion pair-forming
compound [c] and the organoaluminum compound [d] can be contacted at a temperature
of usually -100 to 200 °C, preferably -70 to 100 °C.
[0269] In the present invention, copolymerization of ethylene and the α-olefin of 6 to 20
carbon atoms can be carried out under the conditions of a temperature of usually 40
to 200 °C, preferably 50 to 150 °C, particularly preferably 60 to 120 °C, and a pressure
of atmospheric pressure to 100 kg/cm
2, preferably atmospheric pressure to 50 kg/cm
2, particularly preferably atmospheric pressure to 30 kg/cm
2.
[0270] The copolymerization reaction can be conducted by various polymerization processes,
but it is preferably conducted by a solution polymerization process. In the solution
polymerization process, the aforesaid hydrocarbon solvents are employable as the polymerization
solvents.
[0271] Though the copolymerization can be carried out by any of batchwise, semi-continuous
and continuous processes, it is preferably carried out continuously. The polymerization
can be carried out in two or more stages, each of which is conducted under different
reaction conditions.
[0272] The linear and long-chain branched ethylene/α-olefin random copolymers which are
preferably used in the invention are obtained by the process mentioned above, and
the molecular weight of these copolymers can be modified by controlling the polymerization
conditions such as polymerization temperature or controlling the amount of hydrogen
(molecular weight modifier).
Graft-modified ethylene/α-olefin random copolymer
[0273] As described above, the graft-modified ethylene/α-olefin random copolymer (B) used
in the invention is obtained by graft-modifying the above-described unmodified ethylene/α-olefin
random copolymer with a specific amount of an unsaturated carboxylic acid or its derivative.
[0274] The graft quantity of the unsaturated carboxylic acid or its derivative in the graft-modified
ethylene/α-olefin random copolymer (B) is in the range of 0.01 to 10 % by weight,
preferably 0.1 to 5 % by weight, based on 100 % by weight of the unmodified ethylene/α-olefin
random copolymer.
[0275] The graft-modified ethylene/α-olefin random copolymer (B) having a graft quantity
within the above range exhibits high dispersibility in the polyamide resin composition,
and besides it has excellent heat stability, so that the resin is not colored when
melted. Moreover, when this graft-modified ethylene/α-olefin random copolymer (B)
is used, a polyamide resin composition capable of providing molded products of high
mechanical strength can be obtained.
[0276] Examples of the unsaturated carboxylic acids employable herein include acrylic acid,
maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid,
crotonic acid, isocrotonic acid and Nadic acid™ (endocis-bicyclo[2,2,1]hepto-5-ene-2,3-dicarboxylic
acid).
[0277] Examples of the derivatives of unsaturated carboxylic acids include acid halide compounds,
amide compounds, imide compounds, acid anhydrides and ester compounds of the above-mentioned
unsaturated carboxylic acids. More specifically, there can be mentioned malenyl chloride,
maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate
and glycidyl maleate. Of these, preferable are unsaturated carboxylic acids and anhydrides
thereof, and particularly preferable are maleic acid, Nadic acid™ and anhydrides of
these acids.
[0278] There is no specific limitation on the position of the unmodified ethylene/α-olefin
random copolymer, at which the copolymer is grafted with the unsaturated carboxylic
acid or its derivative, and it is enough that the unsaturated carboxylic acid or its
derivative is bonded to an arbitrary carbon atom of the ethylene/α-olefin random copolymer
for forming the graft-modified ethylene/α-olefin random copolymer (B).
[0279] The graft-modified ethylene/α-olefin random copolymer (B) can be prepared by various
processes conventionally known, for example, the following processes.
(1) Melting the unmodified ethylene/α-olefin random copolymer, to the molten copolymer
is added the unsaturated carboxylic acid or its derivative to perform graft copolymerization.
(2) Dissolving the unmodified ethylene/α-olefin random copolymer in a solvent, to
the obtained solution is added the unsaturated carboxylic acid or its derivative to
perform graft copolymerization.
[0280] In any of the above processes, the graft reaction is preferably carried out in the
presence of a radical initiator to efficiently graft copolymerize graft monomers such
as the unsaturated carboxylic acid.
[0281] Examples of the radical initiators include organic peroxides and azo compounds. More
specifically, there can be mentioned:
organic peroxides, such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide,
di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(peroxybenzoate)hexyne-3, 1,4-bis(tert-butylperoxyisopropyl)benzene,
lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,
2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl perbenzoate, tert-butyl perphenylacetate,
tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumyl
perpivalate and tert-butyl perdiethylacetate; and
azo compounds, such as azobisisobutyronitrile and dimethylazoisobutyrate.
[0282] Of these, preferably used are dialkyl peroxides such as dicumyl peroxide, di-tert-butyl
peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane
and 1,4-bis(tert-butylperoxyisopropyl)benzene.
[0283] The radical initiator is used in an amount of usually 0.001 to 1 part by weight,
preferably 0.003 to 0.5 part by weight, more preferably 0.05 to 0.3 part by weight,
based on 100 parts by weight of the unmodified ethylene/α-olefin random copolymer.
[0284] The graft reaction using or not using the radical initiator is carried out at a temperature
of usually 60 to 350 °C, preferably 150 to 300 °C.
[0285] In the present invention, the graft-modified ethylene/α-olefin random copolymer (B)
is used in an amount of 5 to 200 parts by weight, preferably 10 to 100 parts by weight,
more preferably 10 to 60 parts by weight, based on 100 parts by weight of the polyamide
resin (A).
[0286] When the graft-modified ethylene/α-olefin random copolymer (B) is used in the above-mentioned
amount, a polyamide resin composition having good moldability and capable of providing
molded products of excellent flexibility, low-temperature impact resistance, resistance
to water-absorption and resistance to saline solutions can be obtained.
Other additives
[0287] To the polyamide resin composition of the invention comprising the polyamide resin
(A) and the graft-modified ethylene/α-olefin random copolymer (B), various additives
such as antioxidant, ultraviolet light absorber, light-protective agent, phosphite
stabilizer, peroxide decomposer, basic co-stabilizer, nucleating agent, plasticizer,
lubricant, antistatic agent, flame retardant, pigment, dye and filler can be optionally
added within limits not prejudicial to the object of the invention. Further, other
polymers may be added to the polyamide resin composition of the invention, within
limits not prejudicial to the object of the invention.
[0288] Examples of the fillers include carbon black, asbestos, talc, silica and silica alumina.
Preparation of polyamide resin composition
[0289] The polyamide resin composition of the invention can be prepared by melt mixing the
polyamide resin (A), the graft-modified ethylene/α-olefin random copolymer (B), and
optionally, additives, by various methods conventionally, known.
[0290] That is, the polyamide resin composition of the invention can be obtained by simultaneously
or successively introducing the above components into a mixing device such as Henschel
mixer, V-type blender, tumbling mixer or ribbon blender to mix them in the device
and then melt kneading the mixture thus obtained by a kneading device such as single-screw
extruder, multi-screw extruder, kneader or Banbury mixer.
[0291] Of the kneading devices, those of good kneading performance such as multi-screw extruder,
kneader and Banbury mixer are preferably used, whereby a polyamide resin composition
of high quality wherein the components are homogeneously dispersed can be obtained.
[0292] In any of the stages, the above-mentioned additives, e.g., antioxidant, can be optionally
added.
[0293] The polyamide resin composition of the invention obtained as above can be molded
into various shapes by various melt molding methods conventionally known such as injection
molding, extrusion molding and compression molding.
EFFECT OF THE INVENTION
[0294] The polyamide resin composition of the invention comprises a specific amount of the
polyamide resin (A) and a specific amount of the graft-modified ethylene/α-olefin
random copolymer (B) which is obtained by graft-modifying an ethylene/α-olefin random
copolymer of ethylene and an α-olefin of 6 to 2C carbon atoms with an unsaturated
carboxylic acid or its derivative and has a graft quantity of 0.01 to 10 % by weight.
The graft-modified ethylene/α-olefin random copolymer (B) is a graft-modified product
of an ethylene/α-olefin random copolymer having a specific α-olefin content and a
specific intrinsic viscosity. Hence, the polyamide resin composition of the invention
has excellent melt flowability, i.e., excellent moldability, and a capability of providing
molded products of excellent flexibility, low-temperature impact resistance, resistance
to water absorption and resistance to saline solutions.
EXAMPLE
[0295] The present invention will be further described with reference to the following examples,
but it should be construed that the invention is in no way limited to those examples.
Example 1
Preparation of ethylene/1-octene random copolymer Preparation of catalyst solution
[0296] To a glass flask thoroughly purged with nitrogen, 0.5 mg of bis(1,3-dimethylcyclopentadienyl)zirconium
chloride was introduced. To the flask were then added 1.57 ml of a toluene solution
of methylaluminooxane (Al: 1.1 mol/l) and 2.76 ml of toluene to obtain a catalyst
solution.
Polymerization
[0297] To a 2 liter stainless steel autoclave thoroughly purged with nitrogen, 600 ml of
hexane and 300 ml of 1-octene were introduced, and the temperature of the system was
elevated to 60 °C. Then, 1 mmol of triisobutylaluminum and 0.5 ml (0.001 mmol in terms
of Zr) of the catalyst solution prepared above were injected into the autoclave together
with ethylene to initiate polymerization. Thereafter, only ethylene was continuously
fed to maintain the total pressure at 3.0 kg/cm
2-G, and the polymerization was continued at 70 °C for 60 minutes. After a small amount
of ethanol was fed to the system to terminate the polymerization, the unreacted ethylene
was purged out. The reaction solution was introduced into a large excess of methanol
to precipitate a polymer. The polymer was separated by filtration and dried overnight
under reduced pressure to obtain a linear ethylene/1-octene random copolymer.
[0298] The copolymer thus obtained had a 1-octene content of 17 % by mol, an intrinsic viscosity
(η), as measured in decalin at 135 °C, of 2.2 dl/g, a glass transition temperature
(Tg) of -60 °C, a crystallinity, as measured by X-ray diffractometry, of 2 %, a molecular
weight distribution (Mw/Mn), as determined by GPC, of 2.5, a B value of 1.1, and a
gη* value of 1.0.
Preparation of maleic anhydride graft-modified ethylene/1-octene random copolymer
[0299] In a Henschel mixer, 10 kg of the linear ethylene/1-octene random copolymer was blended
with a solution obtained by dissolving 50 g of maleic anhydride and 3 g of di-tert-butyl
peroxide in 30 g of acetone.
[0300] Then, the blend obtained above was fed to a single-screw extruder having a screw
diameter of 40 mm and L/D of 26 through a hopper and extruded into strands under the
conditions of a resin temperature of 280 °C and an extrusion rate of 6 kg/hr. The
strands were cooled with water and then pelletized to obtain a maleic anhydride graft-modified
ethylene/1-octene random copolymer.
[0301] From the graft-modified ethylene/1-octene random copolymer, the unreacted maleic
anhydride was extracted with acetone. Then, a graft quantity of the maleic anhydride
in the graft-modified ethylene/1-octene random copolymer was measured. As a result,
the graft quantity was 0.90 % by weight.
Preparation of polyamide resin composition
[0302] 100 Parts by weight of nylon 6 (Amilan CM1017, available from Toray Industries, Inc.,
MFR (235 °C, load of 2.16 kg) : 33 g/10 min) and 25 parts by weight of the maleic
anhydride graft-modified ethylene/1-octene random copolymer pellets were blended by
means of a Henschel mixer to prepare a dry blend.
[0303] Then, the dry blend was fed to a twin-screw extruder (L/D = 40, diameter: 30 mm)
preset at 245 °C to prepare pellets of a polyamide resin composition.
[0304] The pellets of the polyamide resin composition was dried at 80 °C for 24 hours and
subjected to injection molding under the following conditions to prepare specimens
for property tests.
Injection molding conditions
[0305]
Cylinder temperature: 245 °C
Injection pressure: 400 kg/cm2
Mold temperature: 80 °C
[0306] Subsequently, properties of the polyamide resin composition were evaluated by the
following methods.
(1) Flexural test
[0307] A flexural modulus (FM, kg/cm
2) of a specimen having a thickness of 1/8 inch was measured in accordance with ASTM
D 790. Conditioning of the specimen was carried out at 23 °C for 2 days in a dry state.
(2) Izod impact test
[0308] A notched Izod impact strength of a specimen having a thickness of 1/8 inch was measured
at -40 °C in accordance with ASTM D 256. Conditioning of the specimen was carried
out at 23 °C for 2 days in a dry state.
[0309] The results are set forth in Table 1.
Example 2
[0310] A polyamide resin composition was prepared in the same manner as in Example 1 except
that the amount of the maleic anhydride graft-modified ethylene/1-octene random copolymer
was varied to 100 parts by weight. The flexural modulus and the notched impact strength
of the polyamide resin composition were measured by the methods previously described.
The results are set forth in Table 1.
Example 3
[0311] A catalyst solution was prepared in the same manner as in Example 1 except that rac-dimethylsilylene-bis{1-(2-methyl-4-phenylindenyl)}zirconium
dichloride was used in place of bis(1,3-dimethylcyclopentadienyl)zirconium chloride.
Using this catalyst solution, a long-chain branched ethylene/1-octene random copolymer
was prepared in the same manner as in Example 1.
[0312] The copolymer thus obtained had a 1-octene content of 17 % by mol, an intrinsic viscosity
(η), as measured in decalin at 135 °C, of 1.9 dl/g, a glass transition temperature
of -60 °C, a crystallinity, as measured by X-ray diffractometry, of 2 %, a molecular
weight distribution (Mw/Mn), as determined by GPC, of 2.5, a B value of 1.0, and a
gη* value of 0.86.
[0313] The long-chain branched ethylene/1-octene random copolymer was graft-modified with
maleic anhydride in the same manner as in Example 1 to obtain a graft-modified ethylene/1-octene
random copolymer.
[0314] Using the graft-modified ethylene/1-octene random copolymer, pellets of a polyamide
resin composition were prepared in the same manner as in Example 1. The flexural modulus
and the notched Izod impact strength of the polyamide resin composition were measured
by the methods previously described.
[0315] The results are set forth in Table 1.
Comparative Example 1
Preparation of ethylene/1-butene random copolymer
[0316] In a polymerization reactor, vanadium oxytrichloride and ethylaluminum sesquichloride
were employed as a polymerization catalyst, a mixed gas of ethylene and 1-butene and
a hydrogen gas were fed to hexane serving as a polymerization solvent, and polymerization
of ethylene and 1-butene was continuously carried out under the conditions of a temperature
of 40 °C, a pressure of 5 kg/cm
2 and a residence time of 1 hour. From the reaction solution, the solvent was separated
to obtain an ethylene/1-butene random copolymer as the aimed product.
[0317] The copolymer thus obtained had a 1-butene content of 19 % by mol, an intrinsic viscosity
(η), as measured in decalin at 135 °C, of 2.2 dl/g, a glass transition temperature
of -65 °C, a crystallinity, as measured by X-ray diffractometry, of 2 % and a B value
of 1.1.
Preparation of maleic anhydride graft-modified ethylene/1-butene random copolymer
[0318] In a Henschel mixer, 10 kg of the ethylene/1-butene random copolymer was blended
with a solution obtained by dissolving 50 g of maleic anhydride and 3 g of di-tert-butyl
peroxide in 50 g of acetone.
[0319] Then, the blend obtained above was fed to a single-screw extruder having a screw
diameter of 40 mm and L/D of 26 through a hopper and extruded into strands under the
conditions of a resin temperature of 260 °C and an extrusion rate of 6 kg/hr. The
strands were cooled with water and then pelletized to obtain a maleic anhydride graft-modified
ethylene/1-butene random copolymer. From the solution of the graft-modified ethylene/1-butene
random copolymer, the unreacted maleic anhydride was extracted with acetone. Then,
a graft quantity of the maleic anhydride in the graft-modified ethylene/1-butene random
copolymer was measured. As a result, the graft quantity was 0.43 % by weight.
Preparation of polyamide resin composition
[0320] 100 Parts by weight of nylon 6 (Amilan CM1017, available from Toray Industries, Inc.,
MFR (235 °C, load of 2.16 kg) : 33 g/10 min) and 25 parts by weight of the maleic
anhydride graft-modified ethylene/1-butene random copolymer pellets were blended by
means of a Henschel mixer to prepare a dry blend.
[0321] Then, the dry blend was fed to a twin-screw extruder (L/D = 40, diameter: 30 mm)
preset at 245 °C to prepare pellets of a polyamide resin composition.
[0322] The pellets of the polyamide resin composition was dried at 80 °C for 24 hours and
subjected to injection molding under the following conditions to prepare specimens
for property tests. With respect to the spiral flow, the polyamide resin composition
was injected into a half-round mold (diameter: 3.8 mm) provided with spiral grooves
under the following conditions and the flow distance was measured.
Injection molding conditions
[0323]
Cylinder temperature: 245 °C
Injection pressure: 1,000 kg/cm2
Mold temperature: 80 °C
[0324] Then, using the specimens obtained above, the flexural modulus and the notched Izod
impact strength were measured by the methods previously described.
[0325] The results are set forth in Table 1.
Table 1
|
Unit |
Ex. 1 |
Ex. 2 |
Ex. 3 |
Comp. Ex. 1 |
Ethylene/α-olefin random copolymer |
|
|
|
|
|
Content of α-olefin |
% by mol |
17 |
17 |
17 |
19 |
Intrinsic viscosity (η) |
dl/g |
2.2 |
2.2 |
1.9 |
2.2 |
Glass transition temperature (Tg) |
°C |
-60 |
-60 |
-60 |
-65 |
Crystallinity |
% |
2 |
2 |
2 |
2 |
Mw/Mn |
- |
2.5 |
2.5 |
2.5 |
- |
B value |
- |
1.1 |
1.1 |
1.0 |
1.1 |
gη* value |
- |
1.0 |
1.0 |
0.86 |
- |
Graft-modified product |
|
|
|
|
|
Charge of quantity of MAH |
% by wt. |
0.5 |
0.5 |
0.5 |
0.5 |
Graft quantity of MAH |
% by wt. |
0.48 |
0.48 |
0.50 |
0.43 |
Components of polyamide resin composition |
|
|
|
|
|
Nylon-6 |
parts by weight |
100 |
100 |
100 |
100 |
Modified ethylene/α-olefin copolymer |
parts by weight |
25 |
100 |
25 |
25 |
Properties of polyamide resin composition molded product |
|
|
|
|
|
FM |
kg/cm2 |
19400 |
6500 |
19200 |
18600 |
Notched Izod impact strength |
|
|
|
|
|
23 °C |
kg·cm/cm |
N.B. |
N.B. |
N.B. |
- |
-20 °C |
kg·cm/cm |
N.B. |
N.B. |
N.B. |
- |
-40 °C |
kg·cm/cm |
20 |
N.B. |
18 |
16 |
Remarks:
MAH: maleic anhydride
N.B.: non-breakable |
[0326] The α-olefin for constituting the ethylene/α-olefin copolymer is 1-octene in each
of Examples 1 to 3, and it is 1-butene in Comparative Example 1.